Substituted pyrazoline derivatives, pesticidal compositions and use

ABSTRACT

This invention relates to novel substituted pyrazoline derivatives of the general formula ##STR1## processes for their preparation and their use as pesticides.

BACKGROUND OF THE INVENTION

The invention relates to new substituted pyrazoline derivatives, toprocesses for their preparation, and to their use as pesticides.

It is known that certain substituted pyrazoline derivatives have a goodactivity against animal pests.

In this context, see, for example, DE-A 2,700,258, U.S. Pat. No.4,174,393, DE-A 2,529,689 and US-A 4,070,365.

However, the level of action, or duration of action, of these previouslyknown compounds is not entirely satisfactory in all fields of use, inparticular against certain organisms or when low concentrations areused.

SUMMARY OF THE INVENTION

New substituted pyrazoline derivatives have been found, of the generalformula ##STR2## in which R¹ represents an unsaturated five-memberedheterocycle which contains 1 to 4 nitrogen atoms, which is optionallysubstituted and which is optionally benzo-fused,

R² represents hydrogen, alkyl, optionally substituted cycloalkyl,halogenoalkyl, halogenoalkylthio or alkoxycarbonyl or trialkylsilyl,

R³ represents hydrogen or alkyl,

R⁴ represents hydrogen or alkyl,

R⁵ represents hydrogen, alkyl, phenyl or alkylthio,

R⁶ represents optionally substituted alkyl or optionally substitutedcycloalkyl, or represents the radical ##STR3## where R⁷ and R⁸ can beidentical or different and represent hydrogen, halogen, alkyl, nitro,cyano, halogenoalkyl, alkoxy, halogenoalkoxy, alkylthio,halogenoalkylthio, optionally substituted phenoxy, optionallysubstituted mono- or dialkylamino, optionally substituted cycloalkyl,alkoxycarbonyl, optionally substituted arylthio, alkenyloxy, alkinyl,alkylthionyl, alkylsulphonyl, halogenoalkylthionyl,halogenoalkylsulphonyl or halogenoalkoxycarbonyl, or where R⁷ and R⁸together represent a bivalent radical which optionally contains one ortwo oxygen atoms and which is optionally substituted,

X represents oxygen or sulphur and Y and Z can be identical or differentand represent hydrogen, alkyl, halogen, halogenoalkyl, alkoxy,alkylthio, halogenoalkoxy, halogenoalkylthio, alkoxycarbonyl,halogenoalkoxycarbonyl, optionally substituted aryloxy, optionallysubstituted arylthio, alkenyloxy, alkinyl, alkylthionyl, alkylsulphonyl,halogenoalkylthionyl, halogenoalkylsulphonyl, amino, nitro or cyano, orwhere Y and Z together represent optionally halogen-substituted3,4-methylenedioxy or 3,4-ethylenedioxy.

Furthermore, it has been found that the new substituted pyrazolinederivatives of the general formula (I) ##STR4## in which R¹ representsan unsaturated five-membered heterocycle which contains 1 to 4 nitrogenatoms, which is optionally substituted and which is optionallybenzo-fused,

R² represents hydrogen, alkyl, optionally substituted cycloalkyl,halogenoalkyl, halogenoalkylthio, alkoxycarbonyl or trialkylsilyl,

R³ represents hydrogen or alkyl,

R⁴ represents hydrogen or alkyl,

R⁵ represents hydrogen, alkyl, phenyl or alkylthio,

R⁶ represents optionally substituted alkyl or optionally substitutedcycloalkyl, or represents the radical ##STR5## where R⁷ and R⁸ can beidentical or different and represent hydrogen, halogen, alkyl, nitro,cyano, halogenoalkyl, alkoxy, halogenoalkoxy, alkylthio,halogenoalkylthio, optionally substituted phenoxy, optionallysubstituted mono- or dialkylamino, optionally substituted cycloalkyl,alkoxycarbonyl, optionally substituted arylthio, alkenyloxy, alkinyl,alkylthionyl, alkylsulphonyl, halogenoalkylthionyl,halogenoalkylsulphonyl or halogenoalkoxycarbonyl, or where R⁷ and R⁸together represent a bivalent radical which optionally contains one ortwo oxygen atoms and which is optionally substituted,

X represents oxygen or sulphur and Y and Z can be identical or differentand represent hydrogen, alkyl, halogen, halogenoalkyl, alkoxy,alkylthio, halogenoalkoxy, halogenoalkylthio, alkoxycarbonyl,halogenoalkoxycarbonyl, optionally substituted aryloxy, optionallysubstituted arylthio, alkenyloxy, alkinyl, alkylthionyl, alkylsulphonyl,halogenoalkylthionyl, halogenoalkylsulphonyl, amino, nitro or cyano, orwhere Y and Z together represent optionally halogen-substituted3,4-methylenedioxy or 3,4-ethylenedioxy,

are obtained when

(a) to obtain pyrazoline derivatives of the formula (I) in which R⁵represents hydrogen, pyrazoline derivatives of the formula (II) ##STR6##in which Y, Z, R¹, R², R³ and R⁴ have the above-mentioned meaning arereacted with isocyanates or isothiocyanates of the formula (III)

    X═C═N--R.sup.6                                     (III)

in which X and R⁶ have the abovementioned meaning, if appropriate in thepresence of bases, or when

(b) to obtain pyrazoline derivatives of the formula (I) in which R²represents alkyl, cycloalkyl, halogenoalkyl, halogenoalkylthio,alkoxycarbonyl or trialkylsilyl, compounds of the formula (IV) ##STR7##are reacted with compounds of the formula (V)

    Hal--R.sup.9                                               (V)

in which

Hal represents halogen and

R⁹ represents alkyl, cycloalkyl, halogenoalkyl, halogenoalkylthio oralkoxycarbonyl,

in an anhydrous medium with the addition of a strong base.

Finally, it has been found that the new pyrazoline derivatives of thegeneral formula (I) have a very good activity against pests and, inparticular, have a very good insecticidal and acaricidal activity.

Surprisingly, the substituted pyrazoline derivatives according to theinvention have a considerably more powerful insecticidal activityagainst insects and arachnids which damage plants and parasitizewarm-blooded animals than compounds which are similar chemically andfrom the point of view of their action and which are known from theprior art.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

Formula (I) provides a general definition of the substituted pyrazolinederivatives according to the invention. Preferred compounds of theformula (I) are those in which

R¹ represents a 1H-pyrrol-1-yl, 1H-pyrazol-1-yl, 1H-imidazol-1-yl,2H-1,2,3,-triazol-2-yl, 1H-1,2,3-triazol-1-yl, 1H-1,2,4, -triazol-1-yl,4H-1,2,4-triazol-4-yl, 2H-tetrazol-2-yl or 1H-tetrazol-2-yl radical,each of which is optionally substituted by halogen, alkyl(C₁ -C₆), CN,NO₂, alkoxy(C₁ -C₆)carbonyl, alkyl(C₁ -C₄)thio, alkoxy(C₁ -C₆),halogenoalkyl(C₁ -C₄), halogenoalkyl(C₁ -C₄)thio, halogenoalkoxy(C₁-C₄), dialkyl(C₁ -C₄)amino or dihalogenoamino,

R² represents hydrogen, alkyl(C₁ -C₆), cycloalkyl(C₃ -C₇) which isoptionally substituted by halogen or halogenoalkyl(C₁ -C₄); orhalogenoalkyl(C₁ -C₄)thio, alkoxy(C₁ -C₆)carbonyl or trialkyl(C₁-C₆)silyl,

R³ represents hydrogen or alkyl(C₁ -C₆),

R⁴ represents hydrogen or alkyl(C₁ -C₆),

R⁵ represents hydrogen, alkyl(C₁ -C₆), phenyl or alkyl(C₁ -C₄)thio,

R⁶ represents alkyl(C₁ -C₆) which is optionally substituted by halogen,halogenoalkyl(C₁ -C₄) or halogenoalkoxy(C₁ -C₄), or representscycloalkyl(C₃ -C₇) which is optionally substituted by halogen,halogenoalkyl(C₁ -C₄) halogenoalkoxy(C₁ -C₄), or represents the radical##STR8## where R⁷ and R⁸ can be identical or different and representhydrogen, halogen, alkyl(C₁ -C₆), nitro, cyano, halogenoalkyl(C₁ -C₆),alkoxy(C₁ -C₆), halogenoalkoxy(C₁ -C₆), alkyl(C₁ -C₆)thio, halogenoalkyl(C₁ -C₆)thio, phenoxy or phenylthio each of which is optionallysubstituted by halogen, halogenoalkyl(C₁ -C₆), alkoxy(C₁ -C₆) oralkyl(C₁ -C₆), or represent mono- or dialkylamino each of which has 1 to6 carbon atoms in the alkyl radical and each of which is optionallysubstituted by halogen, alkoxy(C₁ -C₄) or halogenoalkyl(C₁ -C₄), orrepresent cycloalkyl(C₃ -C₇) which is optionally substituted by alkyl(C₁-C₄), alkoxy(C₁ -C₄), halogen or alkyl(C₁ -C₄)thio, or representalkoxy(C₁ -C₆)carbonyl, alkenyl(C₂ -C₆)oxy, alkinyl(C₂ -C₆), alkyl(C₁-C₄)thionyl, alkyl(C₁ -C₄)sulphonyl, halogenoalkyl(C₁ -C₄)thionyl,halogenoalkyl(C₁ -C₄)sulphonyl or halogenoalkoxy(C₁ -C₄)-carbonyl, orwhere R⁷ and R⁸ together represent one of the following bivalentradicals: ##STR9## X represents oxygen or sulphur and Y and Z can beidentical or different and represent hydrogen, alkyl(C₁ -C₆), halogen,halogenoalkyl(C₁ -C₆), alkoxy(C₁ -C₆), alkyl(C₁ -C₆)thio,halogenoalkoxy(C₁ -C₄), halogenoalkyl(C₁ -C₄)thio, alkoxy(C₁-C₄)carbonyl, halogenoalkoxy(C₁ -C₄)-carbonyl, phenoxy or phenylthioeach of which is optionally substituted by halogen, alkyl(C₁ -C₄),alkoxy(C₁ -C₄) or halogenoalkyl(C₁ -C₄), or represent alkenyl(C₂-C₆)oxy, alkinyl(C₂ -C₆), alkyl(C₁ -C₄)-thionyl, alkyl(C₁ -C₄)sulphonyl,halogenoalkyl(C₁ -C₄)thionyl, halogenoalkyl(C₁ -C₄)sulphonyl, mono- ordialkyl(C₁ -C₆)amino each of which is optionally substituted by halogen,alkoxy(C₁ -C₄), halogenoalkyl(C₁ -C₄); or represent nitro or cyano, orwhere Y and Z together represent optionally fluorine-and/orchlorine-substituted 3,4-methylenedioxy or 3,4-ethylenedioxy.

Particularly preferred compound of the formula (I) are those in which

R¹ represents a 1H-pyrrol-1-yl, 1H-pyrazol-1-yl, 1H-imidazol-1-yl,2H-1,2,3-triazol-2-yl, 1H-1,2,3-triazol-1-yl, 1H-1,2,4-triazolyl-(1),4H-1,2,4-triazolyl-(4)-, 2H-tetrazol2-yl, 1H-tetrazol-1-yl, radical,each of which is optionally substituted by fluorine, chlorine, bromine,iodine, alkyl(C₁ -C₄), CN, NO₂, alkoxy(C₁ -C₄)carbonyl, alkyl(C₁-C₃)thio, alkoxy(C₁ -C₄), halogenoalkyl(C₁ -C₃ or halogenoalkyl-(C₁-C₃)thio or halogenoalkoxy(C₁ -C₄)carbonyl,

R² represents hydrogen, alkyl(C₁ -C₄), optionally fluorine-, chlorine-,bromine- or halogenoalkyl(C₁ -C₃)-substituted cycloalkyl(C₃ -C₆),halogenoalkyl(C₁ -C₃), halogenoalkyl(C₁ -C₃)thio alkoxy(C₁ -C₄)carbonylor trialkyl(C₁ -C₄)silyl,

R³ represents hydrogen or alkyl(C₁ -C₄),

R⁴ represents hydrogen or alkyl(C₁ -C₄),

R⁵ represents hydrogen, alkyl(C₁ -C₄), phenyl or alkyl(C₁ -C₃)thio,

R⁶ represents alkyl(C₁ -C₄) which is optionally substituted by fluorine,chlorine, bromine, halogenoalkyl(C₁ -C₃) or halogenoalkoxy(C₁ -C₃), orrepresents cycloalkyl(C₃ -C₆) which is optionally substituted byfluorine, chlorine, bromine, halogenoalkyl(C₁ -C₃) or halogenoalkoxy(C₁-C₃), or represents the radical ##STR10## where R⁷ and R⁸ can beidentical or different and represent hydrogen, fluorine, chlorine,bromine, iodine, alkyl(C₁ -C₄), nitro cyano, halogenoalkyl(C₁ -C₃),alkoxy(C₁ -C₄), halogenoalkoxy(C₁ -C₃), alkyl(C₁ -C₃)thio,halogenoalkyl(C₁ -C₃)thio, or phenoxy which is optionally substituted byfluorine, chlorine, bromine, halogenoalkyl(C₁ -C₃), alkoxy(C₁ -C₃) oralkyl(C₁ -C₃), or represent mono- or dialkylamino each of which has 1 to4 carbon atoms in the alkyl radical and each of which is optionallysubstituted by fluorine, chlorine, bromine, alkoxy(C₁ -C₃) orhalogenoalkyl(C₁ -C₃), or represent cycloalkyl(C₃ -C₆) which isoptionally substituted by alkyl(C₁ -C₃), alkoxy(C₁ -C₃), fluorine,chlorine, bromine or alkyl(C₁ -C₃)thio, or where R⁷ and R⁸ togetherrepresent one of the following bivalent radical: ##STR11## X representsoxygen or sulphur and Y and Z can be identical or different andrepresent hydrogen, alkyl(C₁ -C₄), fluorine, chlorine, bromine, iodine,halogenoalkyl(C₁ -C₄), alkoxy(C₁ -C₄), alkyl(C₁ -C₄)thio,halogenoalkoxy(C₁ -C₃), halogenoalkyl(C₁ -C₃)thio, alkoxy(C₁-C₃)carbonyl, phenoxy or phenylthio each of which is optionallysubstituted by fluorine, chlorine, bromine, alkyl(C₁ -C₃), alkoxy(C₁-C₃) or halogenoalkyl(C₁ -C₃), or represent halogenoalkoxy(C₁-C₃)carbonyl, alkenyl(C₂ -C₄)oxy, alkinyl(C₂ -C₄), alkyl(C₁ -C₃)thionyl,alkyl(C₁ -C₃)sulphonyl, halogenoalkyl(C₁ -C₃)thionyl, halogenoalkyl(C₁-C₃)sulphonyl, nitro or cyano, or where Y and Z together representoptionally fluorine-and/or chlorine-substituted 3,4-methylenedioxy or3,4-ethylenedioxy.

The meaning of halogenoalkyl in the substituents in the radicalshalogenoalkyl, halogenoalkoxy, halogenoalkylthio, halogenoalkylthionyland halogenoalkylsulphonyl contains preferably 1 to 4, in particular 1or 2, carbon atoms and preferably 1 to 5, in particular 1 to 3,identical or different halogen atoms, preferred halogen atoms beingfluorine, chlorine and bromine, especially fluorine and chlorine.Examples which may be mentioned are trifluoromethyl,chlorodifluoromethyl, bromomethyl, 2,2,2-trifluoroethyl andpentafluoroethyl.

The following substituted pyrazoline derivatives of the general formula(I) may be mentioned individually in addition to the compounds mentionedin the Preparation Examples:

    __________________________________________________________________________     ##STR12##                                (I)                                 Y      Z X R.sup.1 R.sup.2                                                                         R.sup.3                                                                          R.sup.4                                                                          R.sup.5                                                                         R.sup.6                                          __________________________________________________________________________    H      H O                                                                                ##STR13##                                                                            H H  H  H                                                                                ##STR14##                                       H      H O                                                                                ##STR15##                                                                            H H  H  H                                                                                ##STR16##                                       4-CF.sub.3                                                                           H O                                                                                ##STR17##                                                                            H H  H  H                                                                                ##STR18##                                       4-CF.sub.3                                                                           H O                                                                                ##STR19##                                                                            H H  H  H                                                                                ##STR20##                                       4-CF.sub.3                                                                           H O                                                                                ##STR21##                                                                            H H  H  H                                                                                ##STR22##                                       4-Br   H O                                                                                ##STR23##                                                                            H H  H  H                                                                                ##STR24##                                       3-CF.sub.3                                                                           H O                                                                                ##STR25##                                                                            H H  H  H                                                                                ##STR26##                                       3-CF.sub.3                                                                           H O                                                                                ##STR27##                                                                            H H  H  H                                                                                ##STR28##                                       4-F    H O                                                                                ##STR29##                                                                            H H  H  H                                                                                ##STR30##                                       4-F    H O                                                                                ##STR31##                                                                            H H  H  H                                                                                ##STR32##                                       4-F    H O                                                                                ##STR33##                                                                            H H  H  H                                                                                ##STR34##                                       4-F    H O                                                                                ##STR35##                                                                            H H  H  H                                                                                ##STR36##                                       4-F    H O                                                                                ##STR37##                                                                            H H  H  H                                                                                ##STR38##                                       4-F    H O                                                                                ##STR39##                                                                            H H  H  H                                                                                ##STR40##                                       4-F    H O                                                                                ##STR41##                                                                            H H  H  H                                                                                ##STR42##                                       4-F    H O                                                                                ##STR43##                                                                            H H  H  H                                                                                ##STR44##                                       4-Cl   H O                                                                                ##STR45##                                                                            H H  H  H                                                                                ##STR46##                                       4-OCHF.sub.2                                                                         H O                                                                                ##STR47##                                                                            H H  H  H                                                                                ##STR48##                                       4-F    H O                                                                                ##STR49##                                                                            H H  H  H                                                                                ##STR50##                                       4-F    H O                                                                                ##STR51##                                                                            H H  H  H                                                                                ##STR52##                                       4-F    H O                                                                                ##STR53##                                                                            H H  H  H                                                                                ##STR54##                                       4-F    H O                                                                                ##STR55##                                                                            H H  H  H                                                                                ##STR56##                                       4-F    H O                                                                                ##STR57##                                                                            H H  H  H                                                                                ##STR58##                                       4-Cl   H O                                                                                ##STR59##                                                                            H H  H  H                                                                                ##STR60##                                       4-Cl   H O                                                                                ##STR61##                                                                            H H  H  H                                                                                ##STR62##                                       4-Cl   H O                                                                                ##STR63##                                                                            H H  H  H                                                                                ##STR64##                                       4-Cl   H O                                                                                ##STR65##                                                                            H H  H  H                                                                                ##STR66##                                       4-OCHF.sub.2                                                                         H O                                                                                ##STR67##                                                                            H H  H  H                                                                                ##STR68##                                       4-OCHF.sub.2                                                                         H O                                                                                ##STR69##                                                                            H H  H  H                                                                                ##STR70##                                       4-OCHF.sub.2                                                                         H O                                                                                ##STR71##                                                                            H H  H  H                                                                                ##STR72##                                       4-OCHF.sub.2                                                                         H O                                                                                ##STR73##                                                                            H H  H  H                                                                                ##STR74##                                       4-OCH.sub.2 CF.sub.3                                                                 H O                                                                                ##STR75##                                                                            H H  H  H                                                                                ##STR76##                                       4-OCH.sub.2 CF.sub.3                                                                 H O                                                                                ##STR77##                                                                            H H  H  H                                                                                ##STR78##                                       4-CF.sub.3                                                                           H O                                                                                ##STR79##                                                                            H H  H  H                                                                                ##STR80##                                       4-CF.sub.3                                                                           H O                                                                                ##STR81##                                                                            H H  H  H                                                                                ##STR82##                                       H      H O                                                                                ##STR83##                                                                            H H  H  H                                                                                ##STR84##                                       4-t.-Butyl                                                                           H O                                                                                ##STR85##                                                                            H H  H  H                                                                                ##STR86##                                       3-CF.sub.3                                                                           H O                                                                                ##STR87##                                                                            H H  H  H                                                                                ##STR88##                                       4-CH.sub.3                                                                           H O                                                                                ##STR89##                                                                            H H  H  H                                                                                ##STR90##                                       4-CH.sub.3                                                                           H O                                                                                ##STR91##                                                                            H H  H  H                                                                                ##STR92##                                       4-Cl   H O                                                                                ##STR93##                                                                            H H  H  H                                                                                ##STR94##                                       4-Cl   H O                                                                                ##STR95##                                                                            H H  H  H                                                                                ##STR96##                                       4-F    H O                                                                                ##STR97##                                                                            H H  H  H                                                                                ##STR98##                                       4-Cl   H O                                                                                ##STR99##                                                                            H CH.sub.3                                                                         H  H                                                                                ##STR100##                                      4-OCHF.sub.2                                                                         H O                                                                                ##STR101##                                                                           H CH.sub.3                                                                         H  H                                                                                ##STR102##                                      4-F    H O                                                                                ##STR103##                                                                           H CH.sub.3                                                                         CH.sub.3                                                                         H                                                                                ##STR104##                                      __________________________________________________________________________

If, for example,

3-(4'-fluorophenyl)-4-(1"H-4"-chloropyrazol-1"-yl)-4,5-dihydropyrazoleand 4-difluoromethoxyphenyl isocyanate are used as starting substances,the course of the reaction of process a) according to the invention canbe represented by the following equation: ##STR105##

If, for example,

4-trifluoromethyl-anilide of3-(4-fluorophenyl)-4-(1H-pyrazol-1-yl)-4,5-dihydro-1-pyrazolecarboxylicacid and 2-iodopropane are used as starting substances, the course ofthe reaction of process b) according to the invention can be representedas follows: ##STR106##

Formula (II) provides a general definition of the pyrazoline derivativesrequired as starting substances for carrying out process (a) accordingto the invention. In this formula (II), R¹, R², R³, R⁴, Y and Zpreferably represent those radicals which have already been mentioned inconnection with the description of the substances of the formula (I)according to the invention as being preferred for these substituents.The pyrazoline derivatives of the formula (II) are new.

They are prepared by reacting compounds of the formula (VI) ##STR107##with hydrazine hydrate in a polar organic solvent, preferably analkanol, at temperatures of from 20° to 80° C., in particular at 30° to60° C.: ##STR108##

Depending on the meaning of the substituents R³ and R⁴, the followingpreparation variants of the starting compounds of the formula (VI) arethe result ##STR109##

a) R³ and R⁴ in the formula (VI) represent hydrogen ##STR110##

In this case, the compound is reacted with a formalin solution in apolar organic solvent, preferably an alkanol and in particular inethanol or methanol, with the addition of small amounts of an organicbase, in particular of piperidine, and with the addition of glacialacetic acid.

b) R³ in the formula (VI) represents alkyl or aryl, and R⁴ representshydrogen: ##STR111##

The process conditions correspond to those of the reaction withformaldehyde.

c) R³ and R⁴ in the formula represent alkyl: ##STR112##

In this case, compound (VI) is first converted into the salt with theaid of a strong base, and this is then reacted with a halide, inparticular an iodide of the formula ##STR113##

The compound of the formula (VII) which is formed in this process isbrominated, and the intermediate of the formula (IX) is subsequentlyprepared by adding a base with the elimination of HBr.

Compounds of formula (II) in which R³ and R⁴ stand for hydrogen can beproduced alternatively by reacting compounds of formula XII withhydrazine-hydrate in a polar solvent, preferably in an alkanol attemperatures between 0° C. and 60° C.: ##STR114##

Compounds of formula (XII) can be produced by reacting compounds offormula VIa with dimethylaminohydrochloride and paraformaldehyde in analkanol at temperatures between 30° and 80° C. and subsequentprecipitation of the salt with an non-polar solvent such as an ether:##STR115##

Some of the compounds of the formula (VIa) are new. They are prepared byreacting the compounds ##STR116## where Y and Z have the abovementionedmeaning and Hal represents halogen with the compounds R¹ --H, with theaid of an organic or inorganic base and with the elimination of hydrogenhalide. The compounds of the formula (X) are known substances.

In process variant b), compounds of the formula (IV) ##STR117## in whichX, Y, Z, R¹, R³, R⁴, R⁵ and R⁶ have the above-mentioned meaning, arereacted with a strong base, preferably an organometallic compound, inparticular with butyl-lithium, in inert organic solvent at temperaturesof from -50° to 0° C., in particular of from -30° C. to -15° C., ifappropriate in the presence of a protective gas atmosphere, inparticular rare-gas atmosphere such as, for example, argon, and theproduct is subsequently reacted with a halide Hal--R² where R²represents alkyl, optionally substituted cycloalkyl, halogenoalkyl,alkoxycarbonyl or halogenoalkylthio,

at 0° to 60° C., in particular at -10° to -40° C., and the product isworked up in the customary manner by adding water and extracting themixture with ether.

This gives compounds of the formula (XI) ##STR118## where X, Y, Z, R¹,R², R³, R⁴, R⁵, R⁶ and R⁹ have the abovementioned meanings.

The active compounds are suitable for combating animal pests, especiallyarthropods and nematodes, in particular insects and arachnids,encountered in agriculture, in animal husbandry, in forestry, in theprotection of stored products and of materials, and in the hygienefield. They are active against normally sensitive and resistant speciesand against all or some stages of development. The abovementioned pestsinclude:

From the order of the Isopoda, for example, Oniscus asellus,Armadillidium vulgare and Porcellio scaber. From the order of theDiplopoda, for example, Blaniulus guttulatus. From the order of theChilopoda, for example, Geophilus carpophagus and Scutigera spec. Fromthe order of the Symphyla, for example, Scutigerella immaculata. Fromthe order of the Thysanura, for example, Lepisma saccharina. From theorder of the Collembola, for example, Onychiurus armatus. From the orderof the Orthoptera, for example, Blatta orientalis, Periplanetaamericana, Leucophaea maderae, Blattella germanica, Acheta domesticus,Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplusdifferentialis and Schistocerca gregaria. From the order of theDermaptera, for example, Forficula auricularia. From the order of theIsoptera, for example, Reticulitermes spp. From the order of theAnoplura, for example, Phylloxera vastatrix, Pemphigus spp., Pediculushumanus corporis, Haematopinus spp. and Linognathus spp. From the orderof the Mallophaga, for example, Trichodectes spp. and Damalinea spp.From the order of the Thysanoptera, for example, Hercinothrips femoralisand Thrips tabaci. From the order of the Heteroptera, for example,Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimexlectularius, Rhodnius prolixus and Triatoma spp. From the order of theHomoptera, for example, Aleurodes brassicae, Bemisia tabaci,Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae,Cryptomyzus ribis, Aphis fabae, Doralis pomi, Eriosoma lanigerum,Hyalopterus arundinis, Macrosiphum avenae, Myzus spp., Phorodon humuli,Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus, Nephotettixcincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus,Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae,Pseudococcus spp. and Psylla spp. From the order of the Lepidoptera, forexample, Pectinophora gossypiella, Bupalus piniarius, Cheimatobiabrumata, Lithocolletis blancardella, Hyponomeuta padella, Plutellamaculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantriaspp. Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spp.,Euxoa spp., Feltia spp., Earias insulana, Heliothis spp., Spodopteraexigua, Mamestra brassicae, Panolis flammea, Prodenia litura, Spodopteraspp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp.,Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Tineolabisselliella, Tinea pellionella, Hofmannophila pseudospretella, Cacoeciapodana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella,Homona magnanima and Tortrix viridana. From the order of the Coleoptera,for example, Anobium punctatum, Rhizopertha dominica, Acanthoscelidesobtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni,Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp.,Psylliodes chrysocephala, Epilachna varive stis, Atomaria spp.,Oryzaephilus surinamensis, Antho nomus spp., Sitophilus spp.,Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchusassimilis, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenusspp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp.,Niptus hololeucus, Gibbium psylloides, Tribolium spp., Tenebrio molitor,Agriotes spp., Cono derus spp., Melolontha melolontha, Amphimallonsolsti tialis and Costelytra zealandica. From the order of theHymenoptera, for example, Diprion spp., Hoplocampa spp., Lasius spp.,Monomorium pharaonis and Vespa spp. From the order of the Diptera, forexample, Aedes spp., Anopheles spp., Culex spp., Drosophilamelanogaster, Musca spp., Hydrotaea spp., Haematobia spp., Glossinaspp., Melophagus spp., Fannia spp., Calliphora erythrocephala, Luciliaspp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppoboscaspp., Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tanniaspp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyiahyoscyami, Ceratitis capitata, Dacus oleae and Tipula paludosa. From theorder of the Siphonaptera, for example, Xenopsylla cheopis Ceratophyllusspp. and Ctenocephalides spp. From the order of the Arachnida, forexample, Scorpio maurus and Latrodectus mactans. From the order of theAcarina, for example, Acarum siro, Argas spp., Ornithodoros spp.,Dermanyssus gallinae, Ornithonyssus spp., Eriophyes ribis,Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyommaspp., Hyalomma spp., Ixodes spp., Dermacentor spp., Haemaphysalis spp.,Otobius spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp.,Psorergates spp., Demodex spp., Notoedres spp., Tarsonemus spp., Bryobiapraetiosa, Panonychus spp. and Tetranychus spp.

The active compounds according to the invention are not only activeagainst plant, hygiene and stored-product pests, but also, in theveterinary medicine sector, against animal parasites (ectoparasites andendoparasites), such as scaly ticks, argasidae, scab mites, trombidae,flies (piercing and sucking), parasitic fly larvae, lice, hair lice,bird lice, fleas and worms which live as endoparasites.

They are active against normally sensitive and resistant species andstrains, as well as against all parasitic and non-parasitic stages ofdevelopment of the ecto- and endoparasites.

The active compounds according to the invention have a stronginsecticidal and acaricidal activity.

They can be employed particularly successfully against insects which areharmful to plants, such as, for example, against the green peach aphid(Myzus persicae), or against the larvae of the mustard beetle (Phaedoncochleariae) or against the larvae of the cabbage moth (Plutellaxylostella), or against the larvae of the green rice leafhopper(Nephotettix cincticeps), or against the larvae of the cotton boll worm(Heliothis armigera), or against the larvae of the army worm (Spodopterafrugiperda); for combating mites which damage plants, such as, forexample, against the common spider mite or the two-spotted spider mite(Tetranychus urticae).

In addition, they can be employed with particularly good success forcombating pests which live as parasites on warm-blooded animals, suchas, for example, against the larvae of the sheep maggot fly (Luciliacuprina), against ticks of cattle (Boophilus microplus) or against scabmites (Psoroptes ovis), and also against cockroaches (Blattellagermanica and the like).

Furthermore, the compounds according to the invention also have anactivity against parasitic protozoa, and in particular against Coccidiaand/or Plasmodium.

The active compounds can be converted to the customary formulations,such as solutions, emulsions, suspensions, powders, foams, pastes,granules, aerosols, natural and synthetic materials impregnated withactive compound, very fine capsules in polymeric substances and incoating compositions for seed, and furthermore in formulations used withburning equipment, such as fumigating cartridges, fumigating cans,fumigating coils and the like, as well as ULV cold mist and warm mistformulations.

These formulations are produced in a known manner, for example by mixingthe active compounds with extenders, that is, liquid solvents, liquefiedgases under pressure, and/or solid carriers, optionally with the use ofsurface-active agents, that is emulsifying agents and/or dispersingagents and/or foam-forming agents. In the case of the use of water as anextender, organic solvents can, for example, also be used as auxiliarysolvents. As liquid solvents, there are suitable in the main: aromatics,such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics orchlorinated aliphatic hydrocarbons, such as chlorobenzenes,chloroethylenes or methylene chloride, aliphatic hydrocarbons, such ascyclohexane or paraffins, for example mineral oil fractions, alcohols,such as butanol or glycol as well as their ethers and esters, ketones,such as acetone, methyl ethyl ketone, methyl isobutyl ketone orcyclohexanone, strongly polar solvents, such as dimethylformamide anddimethyl sulphoxide, as well as water; by liquefied gaseous extenders orcarriers are meant liquids which are gaseous at ambient temperature andunder atmospheric pressure, for example aerosol propellants, such ashalogenohydrocarbons as well as butane, propane, nitrogen and carbondioxide; as solid carriers there are suitable: for example groundnatural minerals, such as kaolins, clays, talc, chalk, quartz,attapulgite, montmorillonite or diatomaceous earth, and ground syntheticminerals, such as highly disperse silica, alumina and silicates; assolid carriers for granules there are suitable: for example crushed andfractionated natural rocks such as calcite, marble, pumice, sepioliteand dolomite, as well as synthetic granules of inorganic and organicmeals, and granules of organic material such as sawdust, coconut shells,maize cobs and tobacco stalks; as emulsifying and/or foam-forming agentsthere are suitable: for example non-ionic and anionic emulsifiers, suchas polyoxyethylene fatty acid esters, polyoxyethylene fatty alcoholethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkylsulphates, arylsulphonates as well as albumen hydrolysis products; asdispersing agents there are suitable: for example lignin-sulphite wasteliquors and methylcellulose.

Adhesives such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, as well as naturalphospholipids, such as cephalins and lecithins, and syntheticphospholipids, can be used in the formulations. Other additives can bemineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyestuffs,such as alizarin dyestuffs, azo dyestuffs and metal phthalocyaninedyestuffs, and trace nutrients such as salts of iron, manganese, boron,copper, cobalt, molybdenum and zinc.

The formulations in general contain between 0.1 and 95 percent by weightof active compound, preferably between 0.5 and 90%.

The active compounds according to the invention can be present in theircommercially available formulations and in the use forms, prepared fromthese formulations, as a mixture with other active compounds, such asinsecticides, attractants, sterilizing agents, acaricides, nematicides,fungicides, growth-regulating substances or herbicides. The insecticidesinclude, for example, phosphoric esters, carbamates, carboxylic esters,chlorinated hydrocarbons, phenylureas and substances produced bymicroorganisms, inter alia.

The active compounds according to the invention can furthermore bepresent in their commercially available formulations and in the useforms, prepared from these formulations, as a mixture with synergisticagents. Synergistic agents are compounds which increase the action ofthe active compounds, without it being necessary for the synergisticagent added to be active itself.

The active compound content of the use forms prepared from thecommercially available formulations can vary within wide limits. Theactive compound concentration of the use forms can be from 0.0000001 to95% by weight of active compound, preferably between 0.0001 and 1% byweight.

The compounds are employed in a customary manner appropriate for the useforms.

When used against hygiene pests and pests of stored products, the activecompounds are distinguished by an excellent residual action on wood andclay as well as by a good stability to alkali on limed substrates.

The active compounds according to the invention are also suitable forcombating insects, mites, ticks etc. in the sectors of animal husbandryand cattle breeding; better results, for example higher milk production,greater weight, more attractive animal pelt, longer life etc., can beachieved by combating the pests.

The application of the active compounds according to the invention iseffected in this sector in a known fashion, such as by externalapplication in the form of, for example, dipping, spraying, pouring-on,spotting-on and dusting, as well as by means of parenteral applicationin the form, for example, of an injection, and, furthermore, by means ofthe feed-through process. In addition, application as moulded articles(collar, ear tag) and application in the form of the so-calledenvironment treatment are also possible.

The biological activity of the compounds according to the invention willbe illustrated with the aid of the following examples.

EXAMPLES Preparation Examples EXAMPLE 1 ##STR119##

2.64 g (0.01 mol) of3-(4'-fluorophenyl)-4-(1"H-4"-chloropyrazol-1"-yl)-4,5-dihydropyrazoleare dissolved at room temperature in 20 ml of anhydrous acetonitrile,and 2 g of 4-difluoromethoxyphenyl isocyanate are added with stirring.The mixture is heated to 50° C., and 2 to 3 drops of triethylamine arethen added. The mixture is subsequently stirred at 50° C. for 1 hours.After the mixture has cooled, the solvent is distilled off in vacuo, and25 ml of ether are added to the residue. The crystals which separate outafter some time are filtered off with suction. 3.1 g of the(4-difluoromethoxy-anilide of3(4'-fluorophenyl)-4-(1"H-4"chloropyrazol-1"-yl)-4,5-dihydro-1-pyrazolecarboxylicacid of melting point 200° C. are obtained.

The following can be prepared in an analogous manner:

    __________________________________________________________________________    General formula                                                                ##STR120##                                                                   Ex. No.                                                                            Y           Z X R.sup.1  R.sup.2                                                                         R.sup.3                                                                         R.sup.4                                                                         R.sup.5                                                                         R.sup.6            M.p.                 __________________________________________________________________________    2    4-F         H O                                                                                ##STR121##                                                                            H H H H                                                                                ##STR122##        oil                  3    4-Cl        H O                                                                                ##STR123##                                                                            H H H H                                                                                ##STR124##        oil                  4    4-Cl        H O                                                                                ##STR125##                                                                            H H H H                                                                                ##STR126##        oil                  5    4-Cl        H O                                                                                ##STR127##                                                                            H H H H                                                                                ##STR128##        149° C.       6    4-F         H O                                                                                ##STR129##                                                                            H H H H                                                                                ##STR130##        Oel                  7    4-Cl        H O                                                                                ##STR131##                                                                            H H H H                                                                                ##STR132##        195-196°                                                               C.                   8    4-Cl        H O                                                                                ##STR133##                                                                            H H H H                                                                                ##STR134##        Oel                  9    4-Cl        H O                                                                                ##STR135##                                                                            H H H H                                                                                ##STR136##        222° C.       10   4-Cl        H O                                                                                ##STR137##                                                                            H H H H                                                                                ##STR138##        Oel                  11   4-Cl        H O                                                                                ##STR139##                                                                            H H H H                                                                                ##STR140##        176° C.       12   4-F         H O                                                                                ##STR141##                                                                            H H H H                                                                                ##STR142##        oil                  13   4-CF        H S                                                                                ##STR143##                                                                            H H H H                                                                                ##STR144##        oil                  14   4-Cl        H S                                                                                ##STR145##                                                                            H H H H                                                                                ##STR146##        oil                  15   4-Cl        H S                                                                                ##STR147##                                                                            H H H H                                                                                ##STR148##        oil                  16   4-OCHF.sub.2                                                                              H O                                                                                ##STR149##                                                                            H H H H                                                                                ##STR150##        oil                  17   4-OCHF.sub.2                                                                              H O                                                                                ##STR151##                                                                            H H H H                                                                                ##STR152##        oil                  17a  4-F         H O                                                                                ##STR153##                                                                            H H H H                                                                                ##STR154##                             18   4-OCHF.sub.2                                                                              H O                                                                                ##STR155##                                                                            H H H H                                                                                ##STR156##                             19   4-OCHF.sub.2                                                                              H S                                                                                ##STR157##                                                                            H H H H                                                                                ##STR158##                             20   4-OCHF.sub.2                                                                              H O                                                                                ##STR159##                                                                            H H H H                                                                                ##STR160##        170-180°                                                               C.                   21   4-Cl        H O                                                                                ##STR161##                                                                            H H H H                                                                                ##STR162##        <250° C.      22   4-Cl        H O                                                                                ##STR163##                                                                            H H H H                                                                                ##STR164##        225° C.       23   4-Cl        H O                                                                                ##STR165##                                                                            H H H H                                                                                ##STR166##        229° C.       24   4-Cl        H O                                                                                ##STR167##                                                                            H H H H                                                                                ##STR168##        233° C.       25   4-Cl        H O                                                                                ##STR169##                                                                            H H H H                                                                                ##STR170##        236-237°                                                               C.                   26   4-Cl        H O                                                                                ##STR171##                                                                            H H H H                                                                                ##STR172##        185° C.       27   4-Cl        H O                                                                                ##STR173##                                                                            H H H H                                                                                ##STR174##        224° C.       28   4-Cl        H O                                                                                ##STR175##                                                                            H H H H                                                                                ##STR176##        225° C.       29   4-Cl        H O                                                                                ##STR177##                                                                            H H H H                                                                                ##STR178##        227° C.       30   4-Cl        H O                                                                                ##STR179##                                                                            H H H H                                                                                ##STR180##        <250° C.      31   4-Cl        H O                                                                                ##STR181##                                                                            H H H H                                                                                ##STR182##        235° C.       32   4-Cl        H O                                                                                ##STR183##                                                                            H H H H                                                                                ##STR184##        245° C.       33   4-Cl        H O                                                                                ##STR185##                                                                            H H H H                                                                                ##STR186##        215° C.       34   4-Cl        H O                                                                                ##STR187##                                                                            H H H H                                                                                ##STR188##        170° C.       35   4-OCHF.sub.2                                                                              H O                                                                                ##STR189##                                                                            H H H H                                                                                ##STR190##        170° C.       36   4-OCHF.sub.2                                                                              H O                                                                                ##STR191##                                                                            H H H H                                                                                ##STR192##        175° C.       37   4-OCHF.sub.2                                                                              H O                                                                                ##STR193##                                                                            H H H H                                                                                ##STR194##        resin                38   4-OCHF.sub.2                                                                              H O                                                                                ##STR195##                                                                            H H H H                                                                                ##STR196##        195° C.       39   4-OCHF.sub.2                                                                              H O                                                                                ##STR197##                                                                            H H H H                                                                                ##STR198##        219° C.       40   4-OCHF.sub.2                                                                              H O                                                                                ##STR199##                                                                            H H H H                                                                                ##STR200##        <230° C.      41   4-OCHF.sub.2                                                                              H O                                                                                ##STR201##                                                                            H H H H                                                                                ##STR202##        resin                42   4-F         H O                                                                                ##STR203##                                                                            H H H H                                                                                ##STR204##        211° C.       43   4-F         H O                                                                                ##STR205##                                                                            H H H H                                                                                ##STR206##        227° C.       44   4-Cl        H O                                                                                ##STR207##                                                                            H H H H                                                                                ##STR208##        216° C.       45   4-Cl        H O                                                                                ##STR209##                                                                            H H H H                                                                                ##STR210##        213° C.       46   4-Cl        H O                                                                                ##STR211##                                                                            H H H H                                                                                ##STR212##        217° C.       47   4-Cl        H O                                                                                ##STR213##                                                                            H H H H                                                                                ##STR214##        <250° C.      48   4-F         H O                                                                                ##STR215##                                                                            H H H H                                                                                ##STR216##        <250° C.      49   4-F         H O                                                                                ##STR217##                                                                            H H H H                                                                                ##STR218##                             50   4-F         H O                                                                                ##STR219##                                                                            H H H H                                                                                ##STR220##        235° C.       51   4-F         H O                                                                                ##STR221##                                                                            H H H H                                                                                ##STR222##        195° C.       52   4-F         H O                                                                                ##STR223##                                                                            H H H H                                                                                ##STR224##        196° C.       53   4-F         H O                                                                                ##STR225##                                                                            H H H H                                                                                ##STR226##        209° C.       54   4-Cl        H O                                                                                ##STR227##                                                                            H H H H                                                                                ##STR228##        179° C.       55   4-Cl        H O                                                                                ##STR229##                                                                            H H H H                                                                                ##STR230##        186° C.       56   4-Cl        H O                                                                                ##STR231##                                                                            H H H H                                                                                ##STR232##        194° C.       57   4-Cl        H O                                                                                ##STR233##                                                                            H H H H                                                                                ##STR234##        245° C.       58   4-Cl        H O                                                                                ##STR235##                                                                            H H H H                                                                                ##STR236##        222° C.       59   4-Cl        H O                                                                                ##STR237##                                                                            H H H H                                                                                ##STR238##        241° C.       60   4-Cl        H O                                                                                ##STR239##                                                                            H H H H                                                                                ##STR240##        239° C.       61   4-Cl        H O                                                                                ##STR241##                                                                            H H H H                                                                                ##STR242##        <250° C.      62   4-OCHF.sub.2                                                                              H O                                                                                ##STR243##                                                                            H H H H                                                                                ##STR244##        207° C.       63   4-OCHF.sub.2                                                                              H O                                                                                ##STR245##                                                                            H H H H                                                                                ##STR246##        192° C.       64   4-OCHF.sub.2                                                                              H O                                                                                ##STR247##                                                                            H H H H                                                                                ##STR248##        170° C.       65   4-OCHF.sub.2                                                                              H O                                                                                ##STR249##                                                                            H H H H                                                                                ##STR250##                             66   4-Cl        H O                                                                                ##STR251##                                                                            H H H H                                                                                ##STR252##        230° C.       67   4-Cl        H O                                                                                ##STR253##                                                                            H H H H                                                                                ##STR254##        198° C.       68   4-Cl        H O                                                                                ##STR255##                                                                            H H H H                                                                                ##STR256##        228- 230°                                                              C.                   69   4-OCHF.sub.2                                                                              H O                                                                                ##STR257##                                                                            H H H H                                                                                ##STR258##        215-225°                                                               C.                   70   4-Cl        H O                                                                                ##STR259##                                                                            H H H H                                                                                ##STR260##                             71   4-Cl        H O                                                                                ##STR261##                                                                            H H H H                                                                                ##STR262##        oil                  72   4-F         H O                                                                                ##STR263##                                                                            H H H H                                                                                ##STR264##        191-192°                                                               C.                   73   4-F         H O                                                                                ##STR265##                                                                            H H H H                                                                                ##STR266##        215° C.       74   4-F         H O                                                                                ##STR267##                                                                            H H H H                                                                                ##STR268##        217° C.       75   4-F         H O                                                                                ##STR269##                                                                            H H H H                                                                                ##STR270##        246-248°                                                               C.                   76   4-F         H O                                                                                ##STR271##                                                                            H H H H                                                                                ##STR272##        212° C.       77   4-F         H O                                                                                ##STR273##                                                                            H H H H                                                                                ##STR274##        226°  C.      78   4-F         H O                                                                                ##STR275##                                                                            H H H H                                                                                ##STR276##        225° C.       79   4-F         H O                                                                                ##STR277##                                                                            H H H H                                                                                ##STR278##        200° C.       80   4-Cl        H O                                                                                ##STR279##                                                                            H H H H                                                                                ##STR280##        235° C.       81   4-Cl        H O                                                                                ##STR281##                                                                            H H H H                                                                                ##STR282##        231° C.       82   4-Cl        H O                                                                                ##STR283##                                                                            H H H H                                                                                ##STR284##        233-234°                                                               C.                   83   4-Cl        H O                                                                                ##STR285##                                                                            H H H H                                                                                ##STR286##        227° C.       84   4-Cl        H O                                                                                ##STR287##                                                                            H H H H                                                                                ##STR288##        239-240°                                                               C.                   85   4-Cl        H O                                                                                ##STR289##                                                                            H H H H                                                                                ##STR290##        214° C.       86   4-Cl        H O                                                                                ##STR291##                                                                            H H H H                                                                                ##STR292##        212° C.       87   4-Cl        H O                                                                                ##STR293##                                                                            H H H H                                                                                ##STR294##        207-208°                                                               C.                   88   4-Cl        H O                                                                                ##STR295##                                                                            H H H H                                                                                ##STR296##        212° C.       89   4-Cl        H O                                                                                ##STR297##                                                                            H H H H                                                                                ##STR298##        109° C.       90   4-F         H O                                                                                ##STR299##                                                                            H H H H                                                                                ##STR300##        oil                  91   4-OCF.sub.3 H O                                                                                ##STR301##                                                                            H H H H                                                                                ##STR302##        215-218°                                                               C.                   92   4-Cl        H O                                                                                ##STR303##                                                                            H H H H                                                                                ##STR304##        135° C.       93   4-OCF.sub.3 H O                                                                                ##STR305##                                                                            H H H H                                                                                ##STR306##        250° C.       94   4-OCF.sub.3 H O                                                                                ##STR307##                                                                            H H H H                                                                                ##STR308##        230° C.       95   4-Cl        H O                                                                                ##STR309##                                                                            H H H H                                                                                ##STR310##        250° C.       96   4-Cl        H O                                                                                ##STR311##                                                                            H H H H                                                                                ##STR312##        186° C.       97   4-Cl        H O                                                                                ##STR313##                                                                            H H H H                                                                                ##STR314##        210° C.       98   4-OCF.sub.3 H O                                                                                ##STR315##                                                                            H H H H                                                                                ##STR316##        oil                  99   4-Cl        H O                                                                                ##STR317##                                                                            H H H H                                                                                ##STR318##        <250° C.      100  4-Cl        H O                                                                                ##STR319##                                                                            H H H H                                                                                ##STR320##        210° C.       101  4-OCHF.sub.2                                                                              H O                                                                                ##STR321##                                                                            H H H H                                                                                ##STR322##        216° C.       102  4-OCHF.sub.2                                                                              H O                                                                                ##STR323##                                                                            H H H H                                                                                ##STR324##        246° C.       103  4-OCHF.sub.2                                                                              H O                                                                                ##STR325##                                                                            H H H H                                                                                ##STR326##        231° C.       __________________________________________________________________________    104  4-OCHF.sub.2                                                                              H O                                                                                ##STR327##                                                                            H H H H                                                                                ##STR328##        214° C.       105  4-Cl        H O                                                                                ##STR329##                                                                            H H H H                                                                                ##STR330##        <250° C.      106  4-Cl        H O                                                                                ##STR331##                                                                            H H H H                                                                                ##STR332##        <250° C.      107  4-F         H O                                                                                ##STR333##                                                                            H H H H                                                                                ##STR334##        234° C.       108  4-F         H O                                                                                ##STR335##                                                                            H H H H                                                                                ##STR336##        oil                  109  4-F         H O                                                                                ##STR337##                                                                            H H H H                                                                                ##STR338##        240° C.       110  4-F         H O                                                                                ##STR339##                                                                            H H H H                                                                                ##STR340##        250° C.       111  4-F         H O                                                                                ##STR341##                                                                            H H H H                                                                                ##STR342##        260°  C.      112  4-Cl        H O                                                                                ##STR343##                                                                            H H H H                                                                                ##STR344##        245° C.       113  4-Cl        H O                                                                                ##STR345##                                                                            H H H H                                                                                ##STR346##        247° C.       114  4-Cl        H O                                                                                ##STR347##                                                                            H H H H                                                                                ##STR348##        250° C.       115  4-Cl        H O                                                                                ##STR349##                                                                            H H H H                                                                                ##STR350##        250° C.       116  4-Cl        H O                                                                                ##STR351##                                                                            H H H H                                                                                ##STR352##        243° C.       117  4-F         H O                                                                                ##STR353##                                                                            H H H H                                                                                ##STR354##        <250° C.      118  4-F         H O                                                                                ##STR355##                                                                            H H H H                                                                                ##STR356##        <250° C.      119  4-Cl        H O                                                                                ##STR357##                                                                            H H H H                                                                                ##STR358##        224° C.       120  4-F         H O                                                                                ##STR359##                                                                            H H H H                                                                                ##STR360##        <250° C.      121  4-F         H O                                                                                ##STR361##                                                                            H H H H                                                                                ##STR362##        201-202°                                                               C.                   122  4-F         H O                                                                                ##STR363##                                                                            H H H H                                                                                ##STR364##        201-202°                                                               C.                   123  4-F         H O                                                                                ##STR365##                                                                            H H H H                                                                                ##STR366##        207-208°                                                               C.                   124  4-F         H O                                                                                ##STR367##                                                                            H H H H                                                                                ##STR368##        220-222°                                                               C.                   125  4-F         H O                                                                                ##STR369##                                                                            H H H H                                                                                ##STR370##        193-194°                                                               C.                   126  4-F         H O                                                                                ##STR371##                                                                            H H H H                                                                                ##STR372##        214-215°                                                               C.                   127  4-F         H O                                                                                ##STR373##                                                                            H H H H                                                                                ##STR374##        201° C.       128  4-F         H O                                                                                ##STR375##                                                                            H H H H                                                                                ##STR376##        199° C.       129  4-OCF.sub.2CHFCl                                                                          H O                                                                                ##STR377##                                                                            H H H H                                                                                ##STR378##                             130  4-OCF.sub.2CHFCl                                                                          H O                                                                                ##STR379##                                                                            H H H H                                                                                ##STR380##                             131  4-OCF.sub.2CHFCF.sub.3                                                                    H O                                                                                ##STR381##                                                                            H H H H                                                                                ##STR382##                             132  H           H O                                                                                ##STR383##                                                                            H H H H                                                                                ##STR384##                             133  4-Br        H O                                                                                ##STR385##                                                                            H H H H                                                                                ##STR386##                             134  4-F         H O                                                                                ##STR387##                                                                            H H H H                                                                                ##STR388##        218° C.       135  4-F         H O                                                                                ##STR389##                                                                            H H H H                                                                                ##STR390##        234° C.       136  4-F         H O                                                                                ##STR391##                                                                            H H H H                                                                                ##STR392##        212° C.       137  4-F         H O                                                                                ##STR393##                                                                            H H H H                                                                                ##STR394##        200° C.       138  4-F         H O                                                                                ##STR395##                                                                            H H H H                                                                                ##STR396##        212° C.       139  4-F         H O                                                                                ##STR397##                                                                            H H H H                                                                                ##STR398##        206° C.       140  4-F         H O                                                                                ##STR399##                                                                            H H H H                                                                                ##STR400##        202° C.       141  4-OCH.sub.2 CF.sub.3                                                                      H O                                                                                ##STR401##                                                                            H H H H                                                                                ##STR402##                             142  4-OCF.sub.2CHFCl                                                                          H O                                                                                ##STR403##                                                                            H H H H                                                                                ##STR404##                             143  4-OCF.sub.2CHFCF.sub.3                                                                    H O                                                                                ##STR405##                                                                            H H H H                                                                                ##STR406##                             144  4-OCF.sub.2 Cl                                                                            H O                                                                                ##STR407##                                                                            H H H H                                                                                ##STR408##                             145  4-F         H O                                                                                ##STR409##                                                                            H H H H                                                                                ##STR410##        217° C.       146  4-F         H O                                                                                ##STR411##                                                                            H H H H                                                                                ##STR412##        202° C.       147  4-Cl        H O                                                                                ##STR413##                                                                            H H H H                                                                                ##STR414##        202° C.       148  4-Cl        H O                                                                                ##STR415##                                                                            H H H H                                                                                ##STR416##        199° C.       149  4-Cl        H O                                                                                ##STR417##                                                                            H H H H                                                                                ##STR418##        203° C.       150  4-Cl        H O                                                                                ##STR419##                                                                            H H H H                                                                                ##STR420##        224° C.       151  4-OCF.sub.2CHFCl                                                                          H O                                                                                ##STR421##                                                                            H H H H                                                                                ##STR422##                             152  4-Cl        H O                                                                                ##STR423##                                                                            H H H H                                                                                ##STR424##        214° C.       153  4-OCHF.sub.2                                                                              H O                                                                                ##STR425##                                                                            H H H H                                                                                ##STR426##        206° C.       154  4-OCHF.sub.2                                                                              H O                                                                                ##STR427##                                                                            H H H H                                                                                ##STR428##        226° C.       155  4-OCHF.sub.2                                                                              H O                                                                                ##STR429##                                                                            H H H H                                                                                ##STR430##        205° C.       156  4-Br        H O                                                                                ##STR431##                                                                            H H H H                                                                                ##STR432##        224° C.       157  4-Br        H O                                                                                ##STR433##                                                                            H H H H                                                                                ##STR434##        Harz                 158  4-Br        H O                                                                                ##STR435##                                                                            H H H H                                                                                ##STR436##        211° C.       159  4-Br        H O                                                                                ##STR437##                                                                            H H H H                                                                                ##STR438##        187° C.       160  4-Br        H O                                                                                ##STR439##                                                                            H H H H                                                                                ##STR440##        225° C.       161  4-Br        H O                                                                                ##STR441##                                                                            H H H H                                                                                ##STR442##        215° C.       162  4-Br        H O                                                                                ##STR443##                                                                            H H H H                                                                                ##STR444##        216° C.       163  4-Br        H O                                                                                ##STR445##                                                                            H H H H                                                                                ##STR446##        216° C.       164  4-Br        H O                                                                                ##STR447##                                                                            H H H H                                                                                ##STR448##                             165  4-Br        H S                                                                                ##STR449##                                                                            H H H H                                                                                ##STR450##        161° C.       166  4-Cl        H O                                                                                ##STR451##                                                                            H H H H CH.sub.2CH.sub.2OCH.sub.2CF.sub.3       167  OCHF.sub.2  H O                                                                                ##STR452##                                                                            H H H H CH.sub.2CH.sub.2OCH.sub.2CF.sub.3       168  4-Cl        H O                                                                                ##STR453##                                                                            H H H H                                                                                ##STR454##                             169  OCHF.sub.2  H O                                                                                ##STR455##                                                                            H H H H                                                                                ##STR456##                             170  4-OCF.sub.2CHFCl                                                                          H O                                                                                ##STR457##                                                                            H H H H                                                                                ##STR458##        200° C.       171  4-OCF.sub.2CHFCl                                                                          H O                                                                                ##STR459##                                                                            H H H H                                                                                ##STR460##        210° C.       172  4-OCF.sub.2CHFCl                                                                          H O                                                                                ##STR461##                                                                            H H H H                                                                                ##STR462##        248° C.       173  4-OCF.sub.2CHFCl                                                                          H O                                                                                ##STR463##                                                                            H H H H                                                                                ##STR464##                             174  4-Br        H O                                                                                ##STR465##                                                                            H H H H                                                                                ##STR466##        223° C.       175  4-OCHF.sub.2                                                                              H O                                                                                ##STR467##                                                                            H H H H                                                                                ##STR468##        152° C.       176  4-OCHF.sub.2                                                                              H O                                                                                ##STR469##                                                                            H H H H                                                                                ##STR470##        211° C.       177  4-OCHF.sub.2                                                                              H O                                                                                ##STR471##                                                                            H H H H                                                                                ##STR472##        169° C.       178  4-OCHF.sub.2                                                                              H O                                                                                ##STR473##                                                                            H H H H                                                                                ##STR474##        226° C.       179  4-Br        H O                                                                                ##STR475##                                                                            H H H H                                                                                ##STR476##                             180  4-Br        H O                                                                                ##STR477##                                                                            H H H H                                                                                ##STR478##        202° C.       181  4-Br        H O                                                                                ##STR479##                                                                            H H H H                                                                                ##STR480##        249° C.       182  4-OCHF.sub.2                                                                              H O                                                                                ##STR481##                                                                            H H H H                                                                                ##STR482##        201° C.       183  H           H O                                                                                ##STR483##                                                                            H H H H                                                                                ##STR484##        227° C.       184  4-Cl        H O                                                                                ##STR485##                                                                            H H H H                                                                                ##STR486##        243° C.       185  H           H O                                                                                ##STR487##                                                                            H H H H                                                                                ##STR488##        219° C.       186  4-Br        H O                                                                                ##STR489##                                                                            H H H H                                                                                ##STR490##                             187  4-Br        H O                                                                                ##STR491##                                                                            H H H H                                                                                ##STR492##        208° C.       188  4-Br        H O                                                                                ##STR493##                                                                            H H H H                                                                                ##STR494##        224° C.       189  4-Br        H O                                                                                ##STR495##                                                                            H H H H                                                                                ##STR496##                             190  4-Br        H O                                                                                ##STR497##                                                                            H H H H                                                                                ##STR498##        249° C.       191  4-OCHF.sub.2                                                                              H O                                                                                ##STR499##                                                                            H H H H                                                                                ##STR500##                             __________________________________________________________________________    192  4-OCHF.sub.2                                                                              H O                                                                                ##STR501##                                                                            H H H H                                                                                ##STR502##                             193  4-OCHF.sub.2                                                                              H O                                                                                ##STR503##                                                                            H H H H                                                                                ##STR504##        180° C.       194  4-OCHF.sub.2                                                                              H O                                                                                ##STR505##                                                                            H H H H                                                                                ##STR506##                             195  4-OCHF.sub.2                                                                              H O                                                                                ##STR507##                                                                            H H H H                                                                                ##STR508##                             196  4-OCHF.sub.2                                                                              H O                                                                                ##STR509##                                                                            H H H H                                                                                ##STR510##        201° C.       197  4-Cl        H O                                                                                ##STR511##                                                                            H H H H                                                                                ##STR512##        242° C.       198  4-Cl        H O                                                                                ##STR513##                                                                            H H H H                                                                                ##STR514##        212° C.       199  4-OCHF.sub.2                                                                              H O                                                                                ##STR515##                                                                            H H H H                                                                                ##STR516##        219° C.       200  4-Br        H O                                                                                ##STR517##                                                                            H H H H                                                                                ##STR518##        219° C.       201  4-Br        H O                                                                                ##STR519##                                                                            H H H H                                                                                ##STR520##        217° C.       202  4-OCHF.sub.2                                                                              H O                                                                                ##STR521##                                                                            H H H H                                                                                ##STR522##                             203  4-Br        H O                                                                                ##STR523##                                                                            H H H H                                                                                ##STR524##        Ol                   204  H           H O                                                                                ##STR525##                                                                            H H H H                                                                                ##STR526##        218° C.       205  H           H O                                                                                ##STR527##                                                                            H H H H                                                                                ##STR528##        223° C.       206  H           H O                                                                                ##STR529##                                                                            H H H H                                                                                ##STR530##        245° C.       206a 4-F         H O                                                                                ##STR531##                                                                            H H H H                                                                                ##STR532##                             207  4-OCH.sub.3 H O                                                                                ##STR533##                                                                            H H H H                                                                                ##STR534##        221° C.       208  4-OCH.sub.3 H O                                                                                ##STR535##                                                                            H H H H                                                                                ##STR536##        238° C.       209  4-OCHF.sub.2                                                                              H O                                                                                ##STR537##                                                                            H H H H                                                                                ##STR538##        252° C.       210  4-OCH.sub.3 H O                                                                                ##STR539##                                                                            H H H H                                                                                ##STR540##        221° C.       211  4-OCH.sub.3 H O                                                                                ##STR541##                                                                            H H H H                                                                                ##STR542##        250° C.       212  4-OCH.sub.3 H O                                                                                ##STR543##                                                                            H H H H                                                                                ##STR544##        210° C.       213  4-OCH.sub.3 H O                                                                                ##STR545##                                                                            H H H H                                                                                ##STR546##        201° C.       214  4-OCH.sub.3 H O                                                                                ##STR547##                                                                            H H H H                                                                                ##STR548##        186° C.       215  H           H O                                                                                ##STR549##                                                                            H H H H                                                                                ##STR550##        212° C.       216  H           H O                                                                                ##STR551##                                                                            H H H H                                                                                ##STR552##        233° C.       217  H           H O                                                                                ##STR553##                                                                            H H H H                                                                                ##STR554##        236° C.       218  H           H O                                                                                ##STR555##                                                                            H H H H                                                                                ##STR556##        215° C.       219  H           H O                                                                                ##STR557##                                                                            H H H H                                                                                ##STR558##        245° C.       220  4-OC.sub.2 H.sub.5                                                                        H O                                                                                ##STR559##                                                                            H H H H                                                                                ##STR560##        179° C.       221  4-OC.sub.2 H.sub.5                                                                        H O                                                                                ##STR561##                                                                            H H H H                                                                                ##STR562##        153° C.       222  4-OC.sub.2 H.sub.5                                                                        H O                                                                                ##STR563##                                                                            H H H H                                                                                ##STR564##        176° C.       223  3-CH.sub.3  H O                                                                                ##STR565##                                                                            H H H H                                                                                ##STR566##        224° C.       224  3-CH.sub.3  H O                                                                                ##STR567##                                                                            H H H H                                                                                ##STR568##        190° C.       225                                                                                 ##STR569## H O                                                                                ##STR570##                                                                            H H H H                                                                                ##STR571##        208° C.       226  4-Cl        H O                                                                                ##STR572##                                                                            H H H H                                                                                ##STR573##        164° C.       227  4-OCHF.sub.2                                                                              H O                                                                                ##STR574##                                                                            H H H H                                                                                ##STR575##        Ol                   228  4-Cl        H O                                                                                ##STR576##                                                                            H H H H                                                                                ##STR577##        197° C.       229  4-Cl        H O                                                                                ##STR578##                                                                            H H H H                                                                                ##STR579##        215° C.       230  4-Cl        H O                                                                                ##STR580##                                                                            H H H H                                                                                ##STR581##        248° C.       231  4-Cl        H O                                                                                ##STR582##                                                                            H H H H                                                                                ##STR583##        188° C.       232  4-Cl        H O                                                                                ##STR584##                                                                            H H H H                                                                                ##STR585##        227° C.       233  4-Cl        H O                                                                                ##STR586##                                                                            H H H H                                                                                ##STR587##        234° C.       234  4-Cl        H O                                                                                ##STR588##                                                                            H H H H                                                                                ##STR589##        232° C.       235  4-Cl        H O                                                                                ##STR590##                                                                            H H H H                                                                                ##STR591##        218° C.       236  4-Cl        H O                                                                                ##STR592##                                                                            H H H H                                                                                ##STR593##        188° C.       237  4-Cl        H O                                                                                ##STR594##                                                                            H H H H                                                                                ##STR595##        184° C.       238  H           H O                                                                                ##STR596##                                                                            H H H H                                                                                ##STR597##        234° C.       239  4-Cl        H O                                                                                ##STR598##                                                                            H H H H                                                                                ##STR599##        217° C.       240  4-OCHF.sub.2                                                                              H O                                                                                ##STR600##                                                                            H H H H                                                                                ##STR601##        224° C.       241  4-F         H O                                                                                ##STR602##                                                                            H H H H                                                                                ##STR603##        195° C.       242  4-Cl        H O                                                                                ##STR604##                                                                            H H H H                                                                                ##STR605##        205° C.       243  4-OCHF.sub.2                                                                              H O                                                                                ##STR606##                                                                            H H H H                                                                                ##STR607##        188°  C.      244  H           H O                                                                                ##STR608##                                                                            H H H H                                                                                ##STR609##        >250° C.      245  H           H O                                                                                ##STR610##                                                                            H H H H                                                                                ##STR611##        180° C.       245a H           H O                                                                                ##STR612##                                                                            H H H H                                                                                ##STR613##                             246  H           H O                                                                                ##STR614##                                                                            H H H H                                                                                ##STR615##        201° C.       247                                                                                 ##STR616##   O                                                                                ##STR617##                                                                            H H H H                                                                                ##STR618##        >250° C.      248                                                                                 ##STR619##   O                                                                                ##STR620##                                                                            H H H H                                                                                ##STR621##        226° C.       249  4-Br        H O                                                                                ##STR622##                                                                            H H H H                                                                                ##STR623##        215° C.       250  4-Br        H O                                                                                ##STR624##                                                                            H H H H                                                                                ##STR625##        225° C.       250a H           H O                                                                                ##STR626##                                                                            H H H H                                                                                ##STR627##                             251  4-Br        H O                                                                                ##STR628##                                                                            H H H H                                                                                ##STR629##        222° C.       252  4-Br        H O                                                                                ##STR630##                                                                            H H H H                                                                                ##STR631##        235° C.       252  4-Br        H O                                                                                ##STR632##                                                                            H H H H                                                                                ##STR633##        235° C.       253                                                                                 ##STR634##   O                                                                                ##STR635##                                                                            H H H H                                                                                ##STR636##        >250° C.      254                                                                                 ##STR637##   O                                                                                ##STR638##                                                                            H H H H                                                                                ##STR639##        199° C.       255                                                                                 ##STR640##   O                                                                                ##STR641##                                                                            H H H H                                                                                ##STR642##        178° C.       256  4-OCHF.sub.2                                                                              H O                                                                                ##STR643##                                                                            H H H H                                                                                ##STR644##                             257  H           H O                                                                                ##STR645##                                                                            H H H H                                                                                ##STR646##        170° C.       258  H           H O                                                                                ##STR647##                                                                            H H H H                                                                                ##STR648##        235° C.       259  H           H O                                                                                ##STR649##                                                                            H H H H                                                                                ##STR650##        208° C.       259a                                                                                ##STR651## H O                                                                                ##STR652##                                                                            H H H H                                                                                ##STR653##        208° C.       260  4-F         H O                                                                                ##STR654##                                                                            H H H H                                                                                ##STR655##        222° C.       261  H           H O                                                                                ##STR656##                                                                            H H H H                                                                                ##STR657##        198° C.       262  4-OCHF.sub.2                                                                              H O                                                                                ##STR658##                                                                            H H H H                                                                                ##STR659##        235° C.       263  4-Cl        H O                                                                                ##STR660##                                                                            H H H H                                                                                ##STR661##        192° C.       264  3,4-OCH.sub.3                                                                             H O                                                                                ##STR662##                                                                            H H H H                                                                                ##STR663##        216° C.       265  3-Cl        H O                                                                                ##STR664##                                                                            H H H H                                                                                ##STR665##        192° C.       266  3-Cl        H O                                                                                ##STR666##                                                                            H H H H                                                                                ##STR667##        195° C.       267  4-OCF.sub.3 H O                                                                                ##STR668##                                                                            H H H H                                                                                ##STR669##        178° C.       268  4-OCF.sub.3 H O                                                                                ##STR670##                                                                            H H H H                                                                                ##STR671##        174° C.       269  4-OCF.sub.3 H O                                                                                ##STR672##                                                                            H H H H                                                                                ##STR673##        170° C.       270  4-CF.sub.3  H O                                                                                ##STR674##                                                                            H H H H                                                                                ##STR675##        233° C.       271  4-CF.sub.3  H O                                                                                ##STR676##                                                                            H H H H                                                                                ##STR677##        107° C.       272  4-CF.sub.3  H O                                                                                ##STR678##                                                                            H H H H                                                                                ##STR679##        224° C.       273  4-Cl        H O                                                                                ##STR680##                                                                            H H H H                                                                                ##STR681##        >250° C.      274  4-Cl        H O                                                                                ##STR682##                                                                            H H H H                                                                                ##STR683##        203° C.       274a 4-Cl        H O                                                                                ##STR684##                                                                            H H H H                                                                                ##STR685##                             275  4-Cl        H O                                                                                ##STR686##                                                                            H H H H                                                                                ##STR687##        221° C.       276  4-OCHF.sub.2                                                                              H O                                                                                ##STR688##                                                                            H H H H                                                                                ##STR689##        184° C.       277  4-OCHF.sub.2                                                                              H O                                                                                ##STR690##                                                                            H H H H                                                                                ##STR691##                             277a 4-OCHF.sub.2                                                                              H O                                                                                ##STR692##                                                                            H H H H                                                                                ##STR693##                             277b 4-F         H O                                                                                ##STR694##                                                                            H H H H                                                                                ##STR695##                             277c 4-Cl        H O                                                                                ##STR696##                                                                            H H H H                                                                                ##STR697##                             277d 4-F         H O                                                                                ##STR698##                                                                            H H H H                                                                                ##STR699##                             277e                                                                                ##STR700## H O                                                                                ##STR701##                                                                            H H H H                                                                                ##STR702##                             __________________________________________________________________________

EXAMPLE 278 ##STR703##

5 g (0.012 mol) of the 4-trifluoromethylanilide of3-(4-fluorophenyl)-4-(1H-pyrazol-1-yl)-4,5-dihydro-1-pyrazolecarboxylicacid are dissolved in 80 ml of (anhydrous) tetrahydrofuran, and 16.5 ml(0.026 mol) of a 15-percent butyllithium solution in hexane are addedwith stirring at -15° C. under an argon atmosphere. Stirring iscontinued for one hour at -15° C., and 5 ml (0.05) mol of 2-iodopropaneare then added at -15° C. The reaction mixture is then heated to roomtemperature (about 20° C.), and, after 30 minutes, 50 ml of water areadded. The mixture is subsequently extracted with 100 ml of ether, theether phase is dried, and the solvent is distilled off in vacuo. Theoily residue is chromatographed over silica gel using hexane/acetone(7:3). 3.3 g of the 4-trifluoromethylanilide of3-(4-fluorophenyl)-4-(1H-pyrazol-1-yl)-4-isopropyl-4,5-dihydro-1-pyrazolecarboxylic acid are obtained as acolourless foam. M.p. 125° C.

¹ H-NMR (CDCl₃, TMS, ppm) 8.236 (1H,s), 7.66-7.0 (10H, m), 6.388 (1H,t),4.535-4.378 (2H, q), 3.3-3.2(1H,m), 1.23 (3H, d) and 1.91 (3H, d).

The following can be prepared in an analogous manner:

    __________________________________________________________________________    General Formula                                                                ##STR704##                                         (I)                       Ex.                                                                           No.                                                                              Y    Z X R.sup.1     R.sup.2                                                                             R.sup.3                                                                         R.sup.4                                                                         R.sup.5                                                                         R.sup.6     M.p.                          __________________________________________________________________________    279                                                                              4-F  H O 1H-Pyrazol-1-yl                                                                           CH.sub.3                                                                            H H H                                                                                ##STR705## 182-184° C.            280                                                                              4-Cl H O 1H-Pyrazol-1-yl                                                                           CH.sub.3                                                                            H H H                                                                                ##STR706##                               281                                                                              4-OCHF.sub.2                                                                       H O 1H-Pyrazol-1-yl                                                                           CH.sub.3                                                                            H H H                                                                                ##STR707##                               282                                                                              4-F  H O 1H-Pyrazol-1-yl                                                                           COOCH.sub.3                                                                         H H H                                                                                ##STR708##                               283                                                                              4-OCHF.sub.2                                                                       H O 1H-Pyrazol-1-yl                                                                           COOCH.sub.3                                                                         H H H                                                                                ##STR709##                               284                                                                              4-F  H O 1,2,4-1H-Triazol-1-yl                                                                     CH.sub.3                                                                            H H H                                                                                ##STR710##                               285                                                                              4-F  H O 1,2,4-1H-Triazol-1-yl                                                                      ##STR711##                                                                         H H H                                                                                ##STR712## 135° C.                286                                                                              4-Cl H O 4-Chlor-1H-Pyrazol-1-yl                                                                   CH.sub.3                                                                            H H H                                                                                ##STR713## 180-182° C.            287                                                                              4-F  H O                                                                                ##STR714## COOCH.sub.3                                                                         H H H                                                                                ##STR715## 169° C.                288                                                                              4-F  H O                                                                                ##STR716## Si(CH.sub.3).sub.3                                                                  H H H                                                                                ##STR717## resin                         288a                                                                             4-OCHF.sub.2                                                                       H O                                                                                ##STR718## Si(CH.sub.3).sub.3                                                                  H H H                                                                                ##STR719## resin                         __________________________________________________________________________

Preparation of Starting Compounds EXAMPLE 1A ##STR720##

6 g (0.024 mol) of4'-fluoro-2-(1"H-4"-chloropyrazol-1"-yl)-acrylophenone are dissolved in60 ml of ethanol, and 3 ml of hydrazine hydrate are added with stirring.During this process, the temperature is maintained at 40°-45° C. whilecooling with a water-bath. Stirring is continued for 30 minutes, and theethanol is subsequently distilled off in vacuo. 150 ml of methylenechloride are added to the residue, the mixture is shaken, and themethylene chloride phase is then separated off and dried over magnesiumsulphate. The solvent is subsequently distilled off in vacuo, and theoily residue is crystallized with toluene/ethyl acetate (10:1). 3.5 g of3-(4'-fluorophenyl)-4-(1"H-4"-chloropyrazol-1"-yl)-4,5-dihydropyrazoleare obtained as pale yellow crystals of melting point 127°-128° C.

The following pyrazolines are obtained in an analogous manner:

    __________________________________________________________________________    General formula                                                                ##STR721##                                                                   Ex. No.                                                                            Y            Z R.sup.1       R.sup.2                                                                          R.sup.3                                                                          R.sup.4                                                                          Physical constants                 __________________________________________________________________________    2A   4-OCHF.sub.2 H 1-H-pyrazol-1-yl                                                                            H  H  H  oil                                3A   4-OCHF.sub.2 H 1,2,4-1H-triazol-1-yl                                                                       H  H  H  oil                                4A   4-Cl         H 1H-pyrazol-1-yl                                                                             H  H  H  oil, .sup.1 H-NMR                                                             (CDCl.sub.3): 7.15-                                                           7.55(6H, m) 6.22(1H, s),                                                      6.0(1H, q), 3.73-3.94                                                         (2H, m)                            5A   4-OCHF.sub.2 H 1H-4-chloro-pyrazol-1-yl                                                                    H  H  H  oil, .sup.1 H-NMR                                                             (CDCl.sub.3): 7.61                                                            (2H, d) 7.08(2H, d),                                                          7.33(1H, s), 7.44(1H, s),                                                     6.51(1H, t) 5.92(1H, q),                                                      3.72-3.9(2H, m)                    6A   4-Cl         H 1H-4-chloro-pyrazol-1-yl                                                                    H  H  H  M.p.: 177° C.               7A   4-F          H 1,2,4-1H-triazol-1-yl                                                                       H  H  H  M.p.: 116-118° C.           8A   4-Cl         H 1,2,4-1H-triazol-1-yl                                                                       H  H  H  M.p.: 175° C.               9A   4-F          H 1-H-pyrazol-1-yl                                                                            H  H  H  M.p.: 130° C.               10A  4-OCF.sub.3  H 1,2,4-1H-triazol-1-yl                                                                       H  H  H  oil                                11A  4-Cl         H 3,5-dimethyl-1H-                                                                            H  H  H  oil, .sup.1 H-NMR(CDCl.sub.3,                                                 TMS):                                                  pyrazol-1-yl           17.20-7.40(4H, m) 6,04-                                                       5.98(1H, 1);                                                                  4.19(1H, s); 4.03-3.69(2H, m)                                                 2.20(3H, s); 2.18(3H, s)           12A  4-F          H 3,5-dimethyl-1H-                                                                            H  H  H  oil                                                    pyrazol-1-yl                                              13A  H            H 1H-pyrazol-1-yl                                                                             H  H  H                                     14A  H            H 1,2,4-1H-triazol-1-yl                                                                       H  H  H                                     15A  4-Br         H 1H-pyrazol-1-yl                                                                             H  H  H                                     16A  4-CF.sub.3   H 1H-pyrazol-1-yl                                                                             H  H  H                                     17A  4-CF.sub.3   H 4-chloro-1H-pyrazol-1-yl                                                                    H  H  H                                     18A  4-CF.sub.3   H 1,2,4-1H-triazol-1-yl                                                                       H  H  H                                     19A  4-CF.sub.3   H 1H-pyrazol-1-yl                                                                             H  H  H                                     20A  4-Br         H 1,2,4-1H-Triazol-1-yl                                                                       H  H  H  M.p. 163° C.                21A  4-Br         H 1H-4-Chlor-pyrazol-1-yl                                                                     H  H  H  M.p. 189° C.                22A  4-F          H 1,2,3,4-2H-Tetrazol-                                                                        H  H  H                                                         2-yl                                                      23A  4-OCH.sub.2 CF.sub.3                                                                       H 1H-Pyrazol-1-yl                                                                             H  H  H                                     24A  4-Cl         H 1,2,4-4H-Triazol-1-yl                                                                       H  H  H                                     25A  4-Cl         H 1,2,4-1H-Triazol-1-yl                                                                       H  CH.sub.3                                                                         H                                     26A  4-F          H 1H-Pyrazol-1-yl                                                                             H  CH.sub.3                                                                         CH.sub.3                              27A  4-OCF.sub.2CHFCl                                                                           H 1H-4-Chlor-pyrazol-1-yl                                                                     H  H  H                                     28A  4-Cl         H                                                                                ##STR722##   H  H  H  Oil                                29A  4-OCHF.sub.2 F                                                                                ##STR723##   H  H  H  Oil                                30A  4-Br         H                                                                                ##STR724##   H  H  H                                     31A  4-OCHF.sub.2 H                                                                                ##STR725##   H  H  H  M.p. 219° C.                32A  H            H                                                                                ##STR726##   H  H  H  M.p. 139° C.                33A  4-Cl         H                                                                                ##STR727##   H  H  H                                     34A  H            H                                                                                ##STR728##   H  H  H                                     35A  4-OCH.sub.3  H                                                                                ##STR729##   H  H  H  Oil                                36A  4-OCH.sub.3  H                                                                                ##STR730##   H  H  H  Oil                                37A  4-OCH.sub.3  H                                                                                ##STR731##   H  H  H  Oil                                38A  4-OCH.sub.3  H                                                                                ##STR732##   H  H  H  Oil                                39A  4-OC.sub.2 H.sub.5                                                                         H                                                                                ##STR733##   H  H  H                                     40A  3-CH.sub.3   H                                                                                ##STR734##   H  H  H  Oil                                41A                                                                                 ##STR735##  H                                                                                ##STR736##   H  H  H  Oil                                42A  4-Cl         H                                                                                ##STR737##   H  H  H                                     43A  4-Cl         H                                                                                ##STR738##   H  H  H                                     44A  4-Br         H                                                                                ##STR739##   H  H  H  M.p. 189° C.                45A                                                                                 ##STR740##                                                                                   ##STR741##   H  H  H  Oil                                46A                                                                                 ##STR742##                                                                                   ##STR743##   H  H  H                                     47A                                                                                 ##STR744##                                                                                   ##STR745##   H  H  H  Oil                                48A  4-F          H                                                                                ##STR746##   H  H  H  Oil                                49A  3,4-OCH.sub.3                                                                              H                                                                                ##STR747##   H  H  H  Oil                                50A  3-Cl         H                                                                                ##STR748##   H  H  H                                     51A  4-OCF.sub.3  H                                                                                ##STR749##   H  H  H                                     52A  4-Cl         H                                                                                ##STR750##   H  H  H                                     53A  4-OCHF.sub.3 H                                                                                ##STR751##   H  H  H                                     __________________________________________________________________________

EXAMPLE 54 A ##STR752##

23.9 g (0.1 mol) of α-(1H-4-chloropyrazol-1-yl)-4'-fluoroacetophenoneare suspended in 30 ml of methanol at 20° to 30° C. 40 ml of 37 percentstrength formalin solution, then 5 ml of piperidine and subsequently 5.5ml of glacial acetic acid are then added with stirring, during whichprocedure the temperature rises to 35° to 40° C. The reaction mixture isthen stirred at room temperature (about 20° C.) for 4 to 5 hours, untilstarting material is no longer present according to a thin-layerchromatography check. The reaction mixture is then diluted with ether to300 ml, and the ether phase is separated off and dried over magnesiumsulphate. For purification, the dried ether phase is filtered oversilica gel. The ether is subsequently distilled off in vacuo. 16 g of ayellow oil are obtained. The resulting4'-fluoro-2-(1"H-4"-chloropyrazol-1" -yl) acrylophenone is furtherreacted without further purification.

¹ H-NMR: (CDCl₃, TMS, ppm) 7.85-7.93 (2H,m); 7.09-7.2 (2H,m); 7.60(1H,s); 7.84 (1H,s); 5.56 (1H,s), 6.34 (1H,s).

The following derivatives can be obtained in an analogous manner:

    __________________________________________________________________________    General formula:                                                               ##STR753##                                                                   Ex.                                   Physical                                No. Y           Z R.sup.1     R.sup.2                                                                         R.sup.3                                                                          R.sup.4                                                                          constants                               __________________________________________________________________________    55A 4-OCHF.sub.2                                                                              H 1,2,4-1H-Triazol-1-yl                                                                       H  H  oil, .sup.1 H-NMR(CDCl.sub.3                                                  8,68(1H, s); 8,06(1H, s),                                                     7,915(2H, d); 7,25(2H, d)                                                     6,63(1H, t), 6,68(1H, s);                                                     5,8(1H, s)                              56A 4-OCHF.sub.2                                                                              H 1H-Pyrazol-1-yl                                                                             H  H  oil                                     57A 4-Cl        H 1H-Pyrazol-1-yl                                                                             H  H  oil                                     58A 4-Cl        H 4-Chlor-1H-pyrazol-1-yl                                                                     H  H  oil, (.sup.1 H-NMR(CDCl.sub.3)                                                6,35(1H, s), 5,58(1H, s)                59A 4-OCHF.sub.2                                                                              H 4-Chlor-1-H-pyrazol-1-yl                                                                    H  H  oil                                     60A 4-F         H 1,2,4-1H-Triazol-1-yl                                                                       H  H  oil, .sup.1 H-NMR(CDCl.sub.3)                                                 8,68(1H, s), 8,05(1H, s),                                                     7,89-7,96(2H, m), 7,24-7,17                                                   (2H, m); 6,67(1H, s); 5.79                                                    (1H, s)                                 61A 4-Cl        H 1,2,4-1H-triazol-1-yl                                                                       H  H  M.p.: 122° C.                    62A 4-OCF.sub.3 H 1,2,4-1H-triazol-1-yl                                                                       H  H  Oil                                     63A 4-Cl        H 3,5-dimethyl-1H-pyrazol-                                                                    H  H  Oil                                                       1-yl                                                        64A 4-F         H 3,5-dimethyl-1H-                                                                            H  H  Oil                                                       pyrazol-1-yl                                                65A 4-F         H 1H-pyrazol-1-yl                                                                             H  H  Oil                                     66A H           H 1H-pyrazol-1-yl                                                                             H  H  Oil                                     67A H           H 1,2,4-1H-triazol-1-yl                                                                       H  H  Oil                                     68A 4-Br        H 1H-pyrazol-1-yl                                                                             H  H  Oil                                     69A 4-CF.sub.3  H 1H-pyrazol-1-yl                                                                             H  H  Oil                                     70A 4-CF.sub.3  H 4-chloro-1H-triazol-1-yl                                                                    H  H  Oil                                     71A 4-CF.sub.3  H 1,2,4-1H-triazol-1-yl                                                                       H  H  Oil                                     72A 4-CH.sub.3  H 1H-pyrazol-1-yl                                                                             H  H  Oil                                     73A 4-OCH.sub.2 CF.sub.3                                                                      H 1H-pyrazol-1-yl                                                                             H  H  Oil                                     74A 4-Br        H imidazol-1-yl H  H  Oil                                     75A 4-Br        H 1H-4-Chlor-pyrazol-1-yl                                                                     H  H                                          76A 4-F         H 1,2,3,4-2H-Tetrazol-1-yl                                                                    H  H  Oil                                     77A 4-Cl        H 1,2,4-1H-Triazol-1-yl                                                                       CH.sub.3                                                                         H  Oil                                     78A 4-F         H 1H-Pyrazol-1-yl                                                                             CH.sub.3                                                                         CH.sub.3                                                                         Oil                                     79A H           H                                                                                ##STR754## H H  H  Oil                                     80A 4-Cl        H                                                                                ##STR755## H H  H  Oil                                     81A H           H                                                                                ##STR756## H H  H  Oil                                     82A 4-OCH.sub.3 H                                                                                ##STR757## H H  H  Oil                                     83A 4-OCH.sub.3 H                                                                                ##STR758## H H  H  Oil                                     84A 4-OCH.sub.3 H                                                                                ##STR759## H H  H  Oil                                     85A 4-OCH.sub.3 H                                                                                ##STR760## H H  H  Oil                                     86A 4-OCH.sub.3 H                                                                                ##STR761## H H  H  Oil                                     87A 3-CH.sub.3  H                                                                                ##STR762## H H  H  Oil                                     88A                                                                                ##STR763## H                                                                                ##STR764## H H  H  Oil                                     89A 4-Cl        H                                                                                ##STR765## H H  H  Oil                                     90A 4-Cl        H                                                                                ##STR766## H H  H  Oil                                     91A 4-Br        H                                                                                ##STR767## H H  H  Oil                                     92A                                                                                ##STR768##                                                                                  ##STR769## H H  H  Oil                                     93A                                                                                ##STR770##                                                                                  ##STR771## H H  H  Oil                                     94A                                                                                ##STR772##                                                                                  ##STR773## H H  H  Oil                                     95A 4-F         H                                                                                ##STR774## H H  H  Oil                                     96A 3,4-OCH.sub.3                                                                             H                                                                                ##STR775## H H  H  Oil                                     97A 3-Cl        H                                                                                ##STR776## H H  H  Oil                                     98A 4-OCF.sub.2 H                                                                                ##STR777## H H  H  Oil                                     Cl                                                                            99A 4-Cl        H                                                                                ##STR778## H H  H  Oil                                     100A.sub.1                                                                        4-OCHF.sub.2                                                                              H                                                                                ##STR779## H H  H  Oil                                     100A.sub.2                                                                        4-OCHF.sub.2                                                                              H                                                                                ##STR780## H H  H  Oil                                     __________________________________________________________________________

EXAMPLE 101A ##STR781##

51.3 g (0.5 mol) of 4-chloropyrazole are dissolved in 700 ml ofacetonitrile, and 150 g of potassium carbonate are added. 100 g ofα-bromo-4-fluoroacetophenone are added to this mixture with stirring,and the mixture is refluxed for four hours, with stirring. Half of thesolvent is subsequently distilled off in vacuo, 500 ml of ether areadded to the residue, and the mixture is then poured into 500 ml ofwater.

The ether phase is separated off and dried over magnesium sulphate, andthe solvent is distilled off in vacuo. 102 g ofα-(1H-4-chloropyrazol-1-yl)-4'-fluoroacetophenone are obtained as acrystalline residue of melting point (M.p.) 136° C.

The following compounds can be obtained in an analogous manner:

    __________________________________________________________________________    Ex. No.                                                                            Formula                  Melting point                                   __________________________________________________________________________    102A                                                                                ##STR782##              122-124° C.                              103A                                                                                ##STR783##              100-102° C.                              104A                                                                                ##STR784##                                                              105A                                                                                ##STR785##                                                              106A                                                                                ##STR786##                                                              107A                                                                                ##STR787##              135-136° C.                              108A                                                                                ##STR788##                                                              109A                                                                                ##STR789##                                                              110A                                                                                ##STR790##                                                              111A                                                                                ##STR791##              105° C.                                  112A                                                                                ##STR792##              134° C.                                  113A                                                                                ##STR793##              148° C.                                  114A                                                                                ##STR794##                                                              115A                                                                                ##STR795##                                                              116A                                                                                ##STR796##                                                              117A                                                                                ##STR797##                                                              118A                                                                                ##STR798##                                                              __________________________________________________________________________

USE EXAMPLES

In the following use examples, the compounds listed below were employedas comparison substances. ##STR799##triflumuron=2-chloro-N[[[4-(trifluoromethoxy)-phenyl]amino]-carbonyl]-benzamide(disclosed in: DE-A 2,601,780) ##STR800## sulprofos=O-ethylO-4-methylthiophenyl S-propyl phosphorodithioate (disclosed in: DE-A2,111,414)

EXAMPLE A Plutella test

Solvent: 3 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent and thestated amount of emulsifier, and the concentrate is diluted with waterto the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into thepreparation of active compound of the desired concentration and areinfested with caterpillars of the diamond-back moth (Plutellamaculipennis) while the leaves are still moist.

After the desired period of time, the destruction in % is determined.100% means that all the caterpillars have been killed; 0% means thatnone of the caterpillars have been killed.

In this test, a superior activity compared with the prior art is shown,for example, by the following compounds of the Preparation Examples: 1,9, 36, 43, 45, 46, 60, 67, 102.

EXAMPLE B Heliothis virescens test

Solvent: 7 parts by weight of dimethylformamide

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent and thestated amount of emulsifier, and the concentrate is diluted with waterto the desired concentration.

Soya shoots (Glycine max) are treated by being dipped into thepreparation of active compound of the desired concentration and areinfested with caterpillars of the tobacco bud worm caterpillar(Heliothis virescens) while the leaves are still moist.

After the desired period of time, the destruction in % is determined.100% means that all the caterpillars have been killed; 0% means thatnone of the caterpillars have been killed.

In this test, a superior activity compared with the prior art is shown,for example, by the following compounds of the Preparation Examples: 9,23, 24, 27, 28, 29, 55, 60, 73, 74, 87, 88, 93, 94.

EXAMPLE C LD₁₀₀ Test

Test animals: Sitophilus granarius

Solvent:

35 parts by weight of ethylene glycol monomethyl ether

35 parts by weight of nonylphenol polyglycol ether

To produce a suitable formulation, three parts by weight of activecompound are mixed with seven parts of the abovementionedsolvent/emulsifier mixture, and the emulsion concentrate thus obtainedis diluted with water to the particular desired concentration.

2 ml of this preparation of active compound are pipetted onto filterpaper dishes (diameter 9.5 cm) which are located in Petri dishes of anappropriate size. After the filter disc has dried, about 30 test animalsare transferred into the Petri dishes and covered.

The state of the test animals is checked 3 days after the experimentshave been set up. The period which is required for a 100% knock-downeffect is determined. If the LD₁₀₀ is not reached after 6 hours, thepercentage of the knocked-down test animals is determined.

In this test, a highly pronounced activity is shown for example by thefollowing compounds of the Preparation Examples: 1, 4, 9, 18, 20, 28,29, 42, 43, 44, 45, 46, 53, 60, 62, 63, 64, 67, 69, 70, 73, 74, 77, 78,79, 80, 82, 83, 86, 93, 94, 122, 123, 140, 145.

EXAMPLE D Test with Lucilia cuprina resistant larvae

Solvent:

35 parts by weight of ethylene glycol monomethyl ether

35 parts by weight of nonylphenol polyglycol ether

To produce a suitable preparation of active compound, three parts byweight of active compound are mixed with seven parts by weight of theabovementioned mixture and the concentrate thus obtained is diluted withwater to the particular desired concentration.

About 20 Lucilia cuprina res. larvae are introduced into a test tubewhich contains approx. 1 cm³ of horse meat and 0.5 ml of the preparationof active compound. After 24 hours, the degree of destruction isdetermined.

In this test, a highly pronounced activity is shown for example by thefollowing compounds of the Preparation Examples: 1, 4, 9, 10, 16, 17,18, 20, 28, 36, 37, 42, 45, 46, 49, 53, 55, 60, 63, 64, 66, 67, 68, 69,73, 74, 83, 93, 94, 104, 122, 123, 140, 145.

EXAMPLE E LD₁₀₀ test

Test animals: Blattella germanica

Solvent:

35 parts by weight of ethylene glycol monomethyl ether

35 parts by weight of nonylphenol polyglycol ether

To produce a suitable formulation, three parts by weight of activecompound are mixed with seven parts of the abovementionedsolvent/emulsifier mixture, and the emulsion concentrate thus obtainedis diluted with water to the particular desired concentration.

2 ml of this preparation of active compound are pipetted onto filterpaper dishes (0 9,5 cm) which are located in Petri dishes of anappropriate size. After the filter discs have dried, 5 test animals aretransferred into the Petri dishes and covered.

The state of the test animals is checked 3 days after the experimentshave been set up. The period which is required for a 100% knock-downeffect is determined. If the LD₁₀₀ is not reached after 6 hours, thepercentage of the knocked-down test animals is determined.

In this test, for example the compounds of Preparation Examples 4, 20,62, 64, 67, 74, 122, 123 and 140 show a highly pronounced activity.

It is understood that the specification and examples are illustrativebut not limitative of the present invention and that other embodimentswithin the spirit and scope of the invention will suggest themselves tothose skilled in the art.

What is claimed is:
 1. Substituted pyrazoline derivatives of the generalformula ##STR801## in which R¹ represents an unsaturated five-memberedheterocycle which contains 1 to 4 nitrogen atoms and which is attachedby way of a ring nitrogen, which is optionally substituted and which isoptionally benzo-fused,R² represents hydrogen, alkyl, optionallysubstituted cycloalkyl, halogenoalkyl, halogenoalkylthio, alkoxycarbonylor trialkylsilyl, R³ represents hydrogen or alkyl, R⁴ representshydrogen or alkyl, R⁵ represents hydrogen, alkyl, phenyl or alkylthio,R⁶ represents optionally substituted alkyl or optionally substitutedcycloalkyl, or represents the radical ##STR802## where R⁷ and R⁸ can beidentical or different and represent hydrogen, halogen, alkyl, nitro,cyano, halogenoalkyl, alkoxy, halogenoalkoxy, alkylthio,halogenoalkylthio, optionally substituted phenoxy, optionallysubstituted mono- or dialkylamino, optionally substituted cycloalkyl,alkoxycarbonyl, optionally substituted arylthio, alkenyloxy, alkinyl,alkylthionyl, alkylsulphonyl, halogenoalkylthionyl,halogenoalkylsulphonyl or halogenoalkoxycarbonyl, or where R⁷ and R⁸together represent a bivalent radical which optionally contains one ortwo oxygen atoms and which is optionally substituted, X representsoxygen or sulphur and Y and Z can be identical or different andrepresent hydrogen, alkyl, halogen, halogenoalkyl, alkoxy, alkylthio,halogenoalkoxy, halogenoalkylthio, alkoxycarbonyl,halogenoalkoxycarbonyl, optionally substituted aryloxy, optionallysubstituted arylthio, alkenyloxy, alkinyl, alkylthionyl, alkylsulphonyl,halogenoalkylthionyl, halogenoalkylsulphonyl, amino, nitro or cyano, orwhere Y and Z together represent optionally halogen-substituted3,4-methylenedioxy or 3,4-ethylenedioxy.
 2. Substituted pyrazolinederivatives according to claim 1, whereinR¹ represents a 1H-pyrrol-1-yl,1H-pyrazol-1-yl, 1H-imidazol-1-yl, 2H-1,2,3-triazol-2-yl,1H-1,2,3-triazol-1-yl, 1H-1,2,4-triazol-1-yl, 4H-1,2,4-triazol-4-yl,2H-tetrazol-2-yl or 1H-tetrazol-2-yl radical, each of which isoptionally substituted by halogen, alkyl(C₁ -C₆), CN, NO₂, alkoxy(C₁-C₆) carbonyl, alkyl(C₁ -C₄)thio, alkoxy(C₁ -C₆), halogenoalkyl(C₁ -C₄),halogenoalkyl(C₁ -C₄)thio, halogenoalkoxy(C₁ -C₄), dialkyl(C₁ -C₄)aminoor dihalogenoamino, R² represents hydrogen, alkyl(C₁ -C₆), cycloalkyl(C₃-C₇) which is optionally substituted by halogen or halogenoalkyl(C₁-C₄); or halogenoalkyl(C₁ -C₄)thio, alkoxy(C₁ -C₆)carbonyl ortrialkyl(C₁ -C₆)silyl, R³ represents hydrogen or alkyl (C₁ -C₆), R⁴represents hydrogen or alkyl(C₁ -C₆), R⁵ represents hydrogen, alkyl(C₁-C₆), phenyl or alkyl (C₁ -C₄)thio, R⁶ represents alkyl(C₁ -C₆) which isoptionally substituted by halogen, halogenoalkyl(C₁ -C₄) orhalogenoalkoxy(C₁ -C₄), or represents cycloalkyl (C₃ -C₇) which isoptionally substituted by halogen, halogenoalkyl (C₁ -C₄),halogenoalkoxy(C₁ -C₄), or represents the radical ##STR803## where R⁷and R⁸ can be identical or different and represent hydrogen, halogen,alkyl(C₁ -C₆), nitro, cyano, halogenoalkyl(C₁ -C₆), alkoxy(C₁ -C₆),halogenoalkoxy(C₁ -C₆), alkyl(C₁ -C₆)thio, halogenoalkyl(C₁ -C₄)thio,phenoxy or phenylthio each of which is optionally substituted byhalogen, halogenoalkyl(C₁ -C₆), alkoxy(C₁ -C₆) or alkyl(C₁ -C₆), orrepresent mono- or dialkylamino each of which has 1 to 6 carbon atoms inthe alkyl radical and each of which is optionally substituted byhalogen, alkoxy(C₁ -C₄) or halogenoalkyl(C₁ -C₄), or representcycloalkyl(C₃ -C₇) which is optionally substituted by alkyl (C₁ -C₄),alkoxy(C₁ -C₄), halogen or alkyl(C₁ -C₄)thio, or represent alkoxy(C₁-C₆)carbonyl, alkenyl(C₂ -C₆)oxy, alkinyl(C₂ -C₆), alkyl(C₁ -C₄)thionyl,alkyl(C₁ -C₄)sulphonyl, halogenoalkyl(C₁ -C₄)-thionyl orhalogenoalkyl(C₁ -C₄) sulphonyl, or where R⁷ and R⁸ together representone of the following bivalent radicals: ##STR804## X represents oxygenor sulphur and Y and Z can be identical or different and representhydrogen, alkyl(C₁ -C₆), halogen, halogenoalkyl(C₁ -C₆), alkoxy(C₁ -C₆),alkyl(C₁ -C₆)thio, halogenoalkoxy(C₁ -C₄), halogenoalkyl(C₁ -C₄)thio,alkoxy(C₁ -C₄)carbonyl, phenoxy or phenylthio each of which isoptionally substituted by halogen, alkyl(C₁ -C₄), alkoxy(C₁ -C₄) orhalogenoalkyl (C₁ -C₄), or represent alkenyl(C₂ -C₆)oxy, alkinyl(C₂-C₆), alkyl(C₁ -C₄)thionyl, alkyl(C₁ -C₄)sulphonyl, halogenoalkyl(C₁-C₄)thionyl, halogenoalkyl(C₁ -C₄)sulphonyl, mono- or dialkyl(C₁-C₆)amino each of which is optionally substituted by halogen, alkoxy(C₁-C₄) or halogenoalkyl(C₁ -C₄), or represent nitro or cyano, or where Yand Z together represent optionally fluorine- and/orchlorine-substituted 3,4-methylenedioxy or 3,4-ethylenedioxy. 3.Substituted pyrazoline derivatives according to claim 1, whereinR¹represents a 1H-pyrrol-1-yl, 1H-pyrazol-1-yl, 1H-imidazol-1-yl,2H-1,2,3,-triazol-2-yl, 1H-1,2,3-triazol-1-yl, 1H-1,2,4-triazol-1-yl,4H-1,2,4-triazol-4-yl, 1-H-1,2,4-triazolyl-(1),4-H-1,2,4-triazolyl-(4)-, 2H-tetrazol-2-yl or 1H-tetrazol-1-yl radical,each of which is optionally substituted by fluorine, chlorine, bromine,iodine, alkyl(C₁ -C₄), CN, NO₂, alkoxy(C₁ -C₄)carbonyl, alkyl(C₁ -C₃)thio, alkoxy(C₁ -C₄), halogenoalkyl(C₁ -C₃), halogenoalkyl(C₁ -C₃)thioor halogenoalkoxy(C₁ -C₄) carbonyl, R² represents hydrogen, alkyl(C₁-C₄), optionally fluorine-, chlorine-, bromine- or halogenoalkyl (C₁-C₃)-substituted cycloalkyl(C₃ -C₆), halogenoalkyl(C₁ -C₃),halogenoalkyl(C₁ -C₃)thio, alkoxy (C₁ -C₄)-carbonyl or trialkyl(C₁-C₄)silyl, R³ represents hydrogen or alkyl(C₁ -C₄), R⁴ representshydrogen or alkyl(C₁ -C₄), R⁵ represents hydrogen, alkyl(C₁ -C₄), phenylor alkyl(C₁ -C₃)thio, R⁶ represents alkyl(C₁ -C₄) which is optionallysubstituted by fluorine, chlorine, bromine, halogenoalkyl(C₁ -C₃) orhalogenoalkoxy(C₁ -C₃), or represents cycloalkyl(C₃ -C₆) which isoptionally substituted by fluorine, chlorine, bromine, halogenoalkyl(C₁-C₃) or halogenoalkoxy(C₁ -C₃), or represents the radical ##STR805##where R⁷ and R⁸ can be identical or different and represent hydrogen,fluorine, chlorine, bromine, iodine, alkyl(C₁ -C₄), nitro, cyano,halogenoalkyl(C₁ -C₃), alkoxy(C₁ -C₄), halogenoalkoxy (C₁ -C₃), alkyl(C₁-C₃)thio, halogenoalkyl(C₁ -C₃)thio, or phenoxy which is optionallysubstituted by fluorine, chlorine, bromine, halogenoalkyl(C₁ -C₃),alkoxy(C₁ -C₃) or alkyl(C₁ -C₃), or represent mono- or dialkylamino eachof which has 1 to 4 carbon atoms in the alkyl radical and each of whichis optionally substituted by fluorine, chlorine, bromine, alkoxy(C₁ -C₃)or halogenoalkyl(C₁ -C₃), or represent cycloalkyl(C₃ -C₆) which isoptionally substituted by alkyl(C₁ -C₃), alkoxy(C₁ -C₃), fluorine,chlorine, bromine or alkyl(C₁ -C₃)thio, or where R⁷ and R⁸ togetherrepresent one of the following bivalent radical: ##STR806## X representsoxygen or sulphur and Y and Z can be identical or different andrepresent hydrogen, alkyl(C₁ -C₄), fluorine, chlorine, bromine, iodine,halogenoalkyl(C₁ -C₄), alkoxy(C₁ -C₄), alkyl(C₁ -C₄)thio,halogenoalkoxy(C₁ -C₃), halogenoalkyl(C₁ -C₃)thio, alkoxy(C₁-C₃)carbonyl, phenoxy or phenylthio each of which is optionallysubstituted by fluorine, chlorine, bromine, alkyl(C₁ -C₃), alkoxy (C₁-C₃) or halogenoalkyl(C₁ -C₃), or represent halogenoalkoxy(C₁-C₃)carbonyl, alkenyl(C₂ -C₄)oxy, alkinyl(C₂ -C₄), alkyl(C₁ -C₃)thionyl, alkyl(C₁ -C₃)sulphonyl, halogenoalkyl C₁ -C₃)thionyl,halogenoalkyl(C₁ -C₃)sulphonyl, nitro or cyano, or where Y and Ztogether represent optionally fluorine- and/or chlorine-substituted3,4-methylenedioxy or 3,4-ethylenedioxy.
 4. Pesticidal compositions,characterized in that they contain at least one substituted pyrazolinederivative according to claim
 1. 5. Method of combating animal pests,characterized in that substituted pyrazoline derivatives according toclaim 1 are allowed to act on animal pests and/or their environment.